JP2016153348A - Hydrogen plasma generation method and hydrogen reduction method using the same - Google Patents
Hydrogen plasma generation method and hydrogen reduction method using the same Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 132
- 239000001257 hydrogen Substances 0.000 title claims abstract description 131
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000011344 liquid material Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
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- 239000007788 liquid Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 230000003247 decreasing effect Effects 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
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- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000010687 lubricating oil Substances 0.000 claims description 5
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 150000002013 dioxins Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006298 dechlorination reaction Methods 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
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- 238000006243 chemical reaction Methods 0.000 description 15
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- 238000009826 distribution Methods 0.000 description 9
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- 238000001228 spectrum Methods 0.000 description 7
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- 150000002500 ions Chemical class 0.000 description 5
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- HZGJTATYGAJRAL-UHFFFAOYSA-N 3,4,4a,5,6,7,8,8a-octahydro-2h-naphthalene-1,1-diol Chemical compound C1CCCC2C(O)(O)CCCC21 HZGJTATYGAJRAL-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000002596 correlated effect Effects 0.000 description 1
- KTHXBEHDVMTNOH-UHFFFAOYSA-N cyclobutanol Chemical compound OC1CCC1 KTHXBEHDVMTNOH-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- YOXHCYXIAVIFCZ-UHFFFAOYSA-N cyclopropanol Chemical compound OC1CC1 YOXHCYXIAVIFCZ-UHFFFAOYSA-N 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
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- Plasma Technology (AREA)
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Abstract
Description
本発明は、水素プラズマの発生方法及びそれを利用した水素還元方法に関する。 The present invention relates to a method for generating hydrogen plasma and a hydrogen reduction method using the method.
イソプロピルアルコール等のアルコールに触媒存在下でマイクロ波を照射すると水素が発生し、発生した水素を利用してポリ塩化ビフェニル（以下ＰＣＢ）を還元分解できることが知られている（例えば特許文献１〜２を参照）。 It is known that when an alcohol such as isopropyl alcohol is irradiated with microwaves in the presence of a catalyst, hydrogen is generated, and polychlorinated biphenyl (hereinafter referred to as PCB) can be reduced and decomposed using the generated hydrogen (for example, Patent Documents 1 and 2). See).
ＰＣＢはその優れた絶縁性能や化学的安定性から変圧器やコンデンサなど多くの電気機器に用いられてきた。しかし１９６８年の「カネミ油症事件」でその有毒性が露見したことを受け、１９７２年には製造及び輸入が禁止され、現在では国内では行政指導のもと、２０２６年までにＰＣＢの処理を完了させることが義務付けられている。ＰＣＢの無害化手法としては真空加熱分離、溶媒洗浄などがある。いずれも大型の容器による集中処理方法であり、オンサイト処理には適していないなどの問題点がある。低温・低圧環境下でオンサイト処理を行う無害化技術としては、２．４５ＧＨｚのマイクロ波（以下ＭＷ）と触媒を用いたＰＣＢ脱塩素化技術が近年適用され始めている（非特許文献１）。この手法のメリットを以下に示す。
１．溶液温度６０℃、大気圧雰囲気という穏やかな環境下で脱塩素化が可能。
２．反応効率が高いため、反応時間を短縮することが可能。
３．副生成物の発生を抑制できる。
PCBs have been used in many electrical devices such as transformers and capacitors because of their excellent insulation performance and chemical stability. However, in response to the exposure of its toxicity in the 1968 “Kanemi oil symptom case”, production and import were banned in 1972, and PCB processing is now complete by 2026 under administrative guidance in Japan. It is mandatory. PCB detoxification methods include vacuum heat separation and solvent cleaning. Both of these are intensive treatment methods using large containers and have problems such as being unsuitable for on-site treatment. As a detoxification technique for performing on-site treatment in a low-temperature and low-pressure environment, a PCB dechlorination technique using a 2.45 GHz microwave (hereinafter referred to as MW) and a catalyst has begun to be applied in recent years (Non-Patent Document 1). The merit of this method is shown below.
1. Dechlorination is possible in a mild environment with a solution temperature of 60 ° C and atmospheric pressure.
2. Because reaction efficiency is high, reaction time can be shortened.
3. Generation of by-products can be suppressed.
ＰＣＢの脱塩素化反応を図１に示す。ＭＷを用いたＰＣＢの脱塩素化反応では、水素供与体であるイソプロピルアルコール（以下ＩＰＡ）から水素が供給される。そしてこの水素がＰＣＢの−Ｃｌ基にアタックすることで、ＣｌをＨに置換しビフェニルへと無害化する。このようにＭＷを用いた脱塩素化反応においては、水素が重要な役割を果たす。しかし、脱塩素化反応に関与する水素の形態や反応のメカニズムについて、その詳細は現在でもわかっていない。 The dechlorination reaction of PCB is shown in FIG. In the PCB dechlorination reaction using MW, hydrogen is supplied from isopropyl alcohol (hereinafter referred to as IPA) which is a hydrogen donor. This hydrogen attacks the -Cl group of the PCB, thereby substituting Cl with H and detoxifying biphenyl. Thus, hydrogen plays an important role in the dechlorination reaction using MW. However, the details of the form of hydrogen involved in the dechlorination reaction and the mechanism of the reaction are still unknown.
本発明者らは、これまでにＭＷによる脱塩素化反応において、水素プラズマが発生しており、水素はラジカルの状態で反応場に供給されていることを明らかにした（非特許文献２、３）。また、水素プラズマ中には高温の電子が含まれ、さらに水素プラズマからは高強度の紫外線も放出される。そのためこれらの要素が脱塩素化反応に有効に作用している可能性もある。 The present inventors have clarified that hydrogen plasma has been generated in the dechlorination reaction by MW so far, and hydrogen is supplied to the reaction field in a radical state (Non-Patent Documents 2 and 3). ). The hydrogen plasma contains high-temperature electrons, and high-intensity ultraviolet rays are also emitted from the hydrogen plasma. Therefore, there is a possibility that these elements are effectively acting in the dechlorination reaction.
本発明は、上記事情に鑑みてなされたものであり、水素プラズマの発生方法及びそれを用いてＰＣＢ等の被処理物質を効率よく還元する水素還元方法を提供することを課題とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for generating hydrogen plasma and a hydrogen reduction method for efficiently reducing a substance to be treated such as PCB using the method.
本発明者等は水素プラズマの特性や有効性を検討すべく、試験管内に発生させた水素プラズマの電子温度を二線強度比法により測定した（非特許文献３参照）。そして、実機と同型のＰＣＢ脱塩素化反応装置と同程度の電界を印加できる簡易的なマイクロ波発生装置を用いて、水素プラズマを発生させ、電子温度・発光頻度を測定した。さらに実際のＰＣＢ脱塩素化反応装置においても同様の試験を行い、新たな知見を得た。 The present inventors measured the electron temperature of hydrogen plasma generated in a test tube by a two-wire intensity ratio method in order to examine the characteristics and effectiveness of hydrogen plasma (see Non-Patent Document 3). Then, using a simple microwave generator capable of applying an electric field of the same level as the PCB dechlorination reactor of the same type as the actual machine, hydrogen plasma was generated, and the electron temperature and the emission frequency were measured. Furthermore, a similar test was performed in an actual PCB dechlorination reactor, and new findings were obtained.
すなわち、本発明は以下の通りである。 That is, the present invention is as follows.
（１）金属触媒の存在下、水素供与体を含有する液状物にマイクロ波を照射し、液状物内の微小バブル中に水素プラズマを発生させることを特徴とする水素プラズマ発生方法。
（２）液状物中の水素供与体の比率を増やすことで水素ラジカル（水素プラズマ中にある水素原子）発生量を減少させ、液状物中の水素供与体の比率を減らすことで水素ラジカル（水素プラズマ中にある水素原子）発生量を増加させるように制御する、上記（１）に記載の水素プラズマ発生方法。
（３）マイクロ波照射強度を高くすることで水素プラズマの発光頻度を高め、マイクロ波照射強度を低くすることで水素プラズマの発光頻度を低くするように制御する、上記（１）に記載の水素プラズマ発生方法。
（４）液状物が、イソプロピルアルコールと炭化水素油を５０：５０〜９０：１０の比率（体積比）で混合した溶液である、上記（１）〜（３）のいずれかに記載の水素プラズマ発生方法。
（５）金属触媒の存在下、被処理物質と水素供与体を含有する液状物にマイクロ波を照射し、液状物内の微小バブル中に水素プラズマを発生させ、電子温度が４，０００ケルビン（Ｋ）以上１５，０００ケルビン（Ｋ）以下の水素プラズマで処理することにより、被処理物質を還元することを特徴とする水素還元方法。
（６）被処理物質が、ＰＣＢ、トリクロロベンゼン、ダイオキシン類、重質油、劣化潤滑油又は二酸化炭素である、上記（５）に記載の水素還元方法。
(1) A hydrogen plasma generation method characterized by irradiating a liquid material containing a hydrogen donor with microwaves in the presence of a metal catalyst to generate hydrogen plasma in microbubbles in the liquid material.
(2) The amount of hydrogen radicals (hydrogen atoms in the hydrogen plasma) is reduced by increasing the proportion of hydrogen donors in the liquid, and the hydrogen radical (hydrogen) by reducing the proportion of hydrogen donors in the liquid. The hydrogen plasma generation method according to (1) above, wherein control is performed so as to increase the generation amount of hydrogen atoms in the plasma).
(3) The hydrogen according to (1), wherein the frequency of hydrogen plasma emission is increased by increasing the microwave irradiation intensity, and the frequency of hydrogen plasma emission is decreased by decreasing the microwave irradiation intensity. Plasma generation method.
(4) The hydrogen plasma according to any one of (1) to (3) above, wherein the liquid is a solution obtained by mixing isopropyl alcohol and hydrocarbon oil in a ratio (volume ratio) of 50:50 to 90:10. Occurrence method.
(5) In the presence of a metal catalyst, a liquid material containing a material to be treated and a hydrogen donor is irradiated with microwaves to generate hydrogen plasma in microbubbles in the liquid material, and an electron temperature of 4,000 Kelvin ( K) A hydrogen reduction method comprising reducing a substance to be treated by treatment with hydrogen plasma of 15,000 Kelvin (K) or less.
(6) The hydrogen reduction method according to (5), wherein the substance to be treated is PCB, trichlorobenzene, dioxins, heavy oil, deteriorated lubricating oil, or carbon dioxide.
本発明に係る水素プラズマ発生方法によれば、水素供与体を含有する液状物にマイクロ波を照射することで、活性の高い水素プラズマ（電子温度１万Ｋ以上）が発生し、水素プラズマの発生量は、水素供与体の比率やマイクロ波照射強度で制御することができる。マイクロ波照射による加熱方法は、ヒータ等の加熱方法に比べて水素発生速度が大きい。よって、ＰＣＢの脱塩素化をはじめとする被処理物質の還元処理において、効率的な水素還元方法を提供できる。 According to the method for generating hydrogen plasma according to the present invention, high-activity hydrogen plasma (electron temperature of 10,000 K or more) is generated by irradiating a liquid substance containing a hydrogen donor with microwaves. The amount can be controlled by the hydrogen donor ratio and the microwave irradiation intensity. A heating method using microwave irradiation has a higher hydrogen generation rate than a heating method such as a heater. Therefore, an efficient hydrogen reduction method can be provided in the reduction treatment of the material to be treated including PCB dechlorination.
以下、本発明を詳細に説明する。本発明において「水素プラズマ」とは、「気泡を構成する水素が部分的に、または完全に電離したもの」の事であり、水素原子や水素イオン、電子が混在している状態を言う。また、「水素ラジカル」とは、「水素プラズマ中にある水素原子」の事であり化学的に活性な粒子を言う。
本発明の水素プラズマ発生方法は、金属触媒の存在下で実施可能である。金属触媒としてはパラジウム、白金、ルテニウム、ロジウム等を、活性炭、グラファイト等に担持させた白金族触媒が好適に用いられる。
マイクロ波を照射する溶液は、水素供与体を含有することが必須である。水素供与体を含有する溶液等の液状物にマイクロ波を照射すると、溶液や液状物内の微小バブル中に水素プラズマを発生させることが可能となる。「液状物」には溶液、スラリー等が含まれる。水素供与体は、還元処理を施す被処理物質を還元するのに必要な最低限量を用いる必要があり、好ましくは希釈溶媒を兼ねて多めに使用することである。水素供与体の液状物全量に対する比率は特に限定されるものではなく、反応速度や反応系の粘性等を考慮すると、体積比率で約５０％以上含有することが望ましい。水素供与体の比率が低いと還元に必要な水素原子数が不足することで、水素プラズマ発生量が減少するおそれがある。水素供与体は、液状物全量に対する体積比率で５０〜９０％程度であることが好ましい。つまり、液状物が水素供与体と炭化水素油から構成される溶液である場合、水素供与体と炭化水素油を５０：５０〜９０：１０（体積比）で混合した溶液が好ましい。
Hereinafter, the present invention will be described in detail. “Hydrogen plasma” in the present invention means “partially or completely ionized hydrogen constituting bubbles”, and means a state in which hydrogen atoms, hydrogen ions, and electrons are mixed. “Hydrogen radical” means “hydrogen atom in hydrogen plasma” and means chemically active particles.
The hydrogen plasma generation method of the present invention can be carried out in the presence of a metal catalyst. As the metal catalyst, a platinum group catalyst in which palladium, platinum, ruthenium, rhodium or the like is supported on activated carbon, graphite or the like is preferably used.
The solution to be irradiated with microwaves must contain a hydrogen donor. When a liquid such as a solution containing a hydrogen donor is irradiated with microwaves, hydrogen plasma can be generated in microbubbles in the solution or liquid. “Liquid” includes solutions, slurries and the like. The hydrogen donor needs to be used in the minimum amount necessary for reducing the substance to be treated to be reduced, and is preferably used in a large amount also as a diluting solvent. The ratio of the hydrogen donor to the total amount of the liquid substance is not particularly limited, and it is preferable to contain about 50% or more by volume ratio in consideration of the reaction rate and the viscosity of the reaction system. If the ratio of the hydrogen donor is low, the number of hydrogen atoms necessary for the reduction is insufficient, which may reduce the amount of hydrogen plasma generated. The hydrogen donor is preferably about 50 to 90% by volume with respect to the total amount of the liquid. That is, when the liquid is a solution composed of a hydrogen donor and a hydrocarbon oil, a solution in which the hydrogen donor and the hydrocarbon oil are mixed at a ratio of 50:50 to 90:10 (volume ratio) is preferable.
水素プラズマ発生時の圧力は、常圧から数百気圧の任意の圧力下で行われ、圧力を上げることによって反応を促進することが可能である。温度は常温から有機溶媒の沸点となる３５０℃程度の任意の温度で行われ、温度を上げることによって反応を促進することが可能である。希釈溶媒の使用は任意であるが、水素供与体を、希釈溶媒を兼ねて用いることが好ましい。
水素供与体としては、複素環式化合物、アミン系化合物、アルコール系化合物、ケトン系化合物、及び脂環式化合物等の有機系水素供与体等が挙げられる。これらの化合物の中でも、安全性が高く、低コストで入手可能であり、しかも反応制御が容易である点より、アルコール系化合物が好ましい。アルコール系化合物の具体例としては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、ｓ−ブタノール、ｔ−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、１−オクタノール、２−オクタノール等の脂肪族アルコール、シクロプロピルアルコール、シクロブチルアルコール、シクロペンチルアルコール、シクロヘキシルアルコール、シクロヘプチルアルコール、シクロオクチルアルコール等の脂環式アルコール、エチレングリコール、プロピレングリコール、デカリンジオール等の多価アルコール等が挙げられる。これらの中でも、２−プロパノール（イソプロピルアルコール）が特に好ましい。水素供与体は、単独で用いても良く、２種以上を任意に組合せて用いても良い。
The pressure at the time of hydrogen plasma generation is performed under an arbitrary pressure from normal pressure to several hundred atm, and the reaction can be promoted by increasing the pressure. The temperature is from an ordinary temperature to an arbitrary temperature of about 350 ° C. which is the boiling point of the organic solvent, and the reaction can be promoted by raising the temperature. The use of a diluting solvent is optional, but it is preferable to use a hydrogen donor also as a diluting solvent.
Examples of the hydrogen donor include organic hydrogen donors such as heterocyclic compounds, amine compounds, alcohol compounds, ketone compounds, and alicyclic compounds. Among these compounds, alcohol compounds are preferable because they are highly safe, can be obtained at low cost, and are easy to control the reaction. Specific examples of the alcohol compound include, for example, methanol, ethanol, 1-propanol, 2-propanol, n-butanol, s-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol and other aliphatic alcohols, cyclopropyl alcohol, cyclobutyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol And cycloaliphatic alcohols such as cycloheptyl alcohol and cyclooctyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol and decalin diol. Among these, 2-propanol (isopropyl alcohol) is particularly preferable. A hydrogen donor may be used independently and may be used in combination of 2 or more types.
本発明の水素プラズマ発生方法においては、液状物中の水素供与体の比率を増やすことで水素ラジカル発生量が減少し、液状物中の水素供与体の比率を減らすことで水素ラジカル発生量が増加する。そのため、水素供与体の比率を制御することで、水素ラジカル発生量を制御することが可能である。
また、本発明の水素プラズマ発生方法においては、マイクロ波照射強度を高くすることで水素プラズマの発光頻度が高くなり、マイクロ波照射強度を低くすることで水素プラズマの発光頻度が低くなる。そのため、マイクロ波照射強度を制御することで、水素プラズマの発光頻度を制御することが可能である。
In the hydrogen plasma generation method of the present invention, the amount of hydrogen radicals generated is decreased by increasing the ratio of hydrogen donors in the liquid material, and the amount of hydrogen radicals generated is increased by decreasing the ratio of hydrogen donors in the liquid material. To do. Therefore, the amount of hydrogen radicals generated can be controlled by controlling the ratio of the hydrogen donor.
In the hydrogen plasma generation method of the present invention, the emission frequency of hydrogen plasma is increased by increasing the microwave irradiation intensity, and the emission frequency of hydrogen plasma is decreased by decreasing the microwave irradiation intensity. Therefore, it is possible to control the emission frequency of hydrogen plasma by controlling the microwave irradiation intensity.
本発明の水素還元方法では、上述した水素プラズマ発生方法を利用する。金属触媒の存在下、被処理物質と水素供与体を含有する液状物にマイクロ波を照射し、液状物内の微小バブル中に水素プラズマを発生させ、被処理物質を還元する。水素還元反応における水素プラズマの電子温度は、水素ラジカルが有効と考えられる反応では、４，０００ケルビン（Ｋ）以上１５，０００ケルビン（Ｋ）以下であり、より好ましくは５，０００Ｋ以上１５，０００Ｋ以下である。反応促進を図る点からは、１０，０００Ｋ以上が好ましい。一方、水素ラジカルだけでなく水素イオン（Ｈ＋）も有効と考えられる反応では、水素プラズマの電子温度は高いほど有利になる（後述の図２参照）。
水素還元方法を実施する場合、例えば、ＰＣＢ脱塩素化反応のような水素が置換する反応では、脱塩素化剤（例えば、水酸化ナトリウム、水酸化カリウム等）を適量使用することが好ましい。また、重質油の軽質化や劣化潤滑油の還元再生を実施する場合は、重質油や劣化潤滑油に水素供与体を添加して液状物とし、該液状物にマイクロ波を照射し、還元処理を施すことができる。
In the hydrogen reduction method of the present invention, the hydrogen plasma generation method described above is used. In the presence of the metal catalyst, the liquid material containing the material to be treated and the hydrogen donor is irradiated with microwaves, hydrogen plasma is generated in the microbubbles in the liquid material, and the material to be treated is reduced. The electron temperature of the hydrogen plasma in the hydrogen reduction reaction is 4,000 Kelvin (K) or more and 15,000 Kelvin (K) or less, more preferably 5,000 K or more and 15,000 K in a reaction in which hydrogen radicals are considered to be effective. It is as follows. In view of promoting the reaction, 10,000 K or more is preferable. On the other hand, in a reaction in which not only hydrogen radicals but also hydrogen ions (H + ) are considered effective, the higher the electron temperature of hydrogen plasma, the more advantageous (see FIG. 2 described later).
When carrying out the hydrogen reduction method, it is preferable to use an appropriate amount of a dechlorinating agent (for example, sodium hydroxide, potassium hydroxide, etc.) in a reaction in which hydrogen is substituted, such as PCB dechlorination reaction. Also, when lightening heavy oil or reducing and regenerating deteriorated lubricating oil, a hydrogen donor is added to the heavy oil or deteriorated lubricating oil to form a liquid, and the liquid is irradiated with microwaves. Reduction treatment can be performed.
次に、実施例により本発明を更に詳細に説明する。また、以下の実施例ではＰＣＢ脱塩素化反応を例に説明するが、本発明は以下の実施例のみに限定されるものではない。 Next, the present invention will be described in more detail with reference to examples. Moreover, although a PCB dechlorination reaction is demonstrated to an example in the following Examples, this invention is not limited only to the following Examples.
［水素プラズマ中粒子組成計算］
ＰＣＢ脱塩素化反応においては、高温の電子と水素ラジカルが重要な役割を果たしていると考えられる。そのため水素プラズマの電子温度と水素の状態を詳細に検討した。検討を行う上での仮定を以下に示す。
１．気泡内のプラズマを構成する粒子は水素分子、原子、イオン、及び電子のみとする。
２．水素プラズマは局所熱平衡状態（ＬＴＥ）にある。
局所熱平衡状態では以下のことが成立する。
２．１ 電子、中性子、イオンの温度が全て等しい。
２．２ 反応平衡が成立（反応速度が無限大）。
２．２．１ 水素原子の電離平衡。
２．２．２ 水素分子の解離平衡。
２．３ 電気的中性。
２．４ 状態方程式。
２．５ 励起準位間のボルツマン分布則。
一般に粒子Ａに対する電離平衡はＳａｈａの式として記述される。
［式１］
分子ＡＢと粒子Ａ、Ｂの解離平衡はＧｕｌｄｂｅｒｇ−Ｗａａｇｅの式として知られている。
［式２］
Ｎは粒子密度、ｋＢはボルツマン定数、ｈはプランク定数、ｇは内部状態和、Ｅｉｏｎは電離エネルギー、Ｅｄｉｓは解離エネルギーである。
電気中性条件と状態方程式はそれぞれ以下のように記述される。
［式３］
［式４］
以上４式からある電子温度ＴにおけるＮＨ２，ＮＨ，ＮＨ＋，Ｎｅ の４粒子の密度を計算できる。これらの式から算出された粒子組成を図２に示す。横軸は電子温度Ｔ［Ｋ］、縦軸は粒子密度Ｎ［ｍ−３］である。
[Calculation of particle composition in hydrogen plasma]
It is considered that high-temperature electrons and hydrogen radicals play an important role in the PCB dechlorination reaction. Therefore, the electron temperature of hydrogen plasma and the state of hydrogen were examined in detail. The assumptions for the examination are shown below.
1. The particles constituting the plasma in the bubbles are only hydrogen molecules, atoms, ions, and electrons.
2. The hydrogen plasma is in local thermal equilibrium (LTE).
The following holds in the local thermal equilibrium state.
2.1 The temperatures of electrons, neutrons, and ions are all equal.
2.2 Reaction equilibrium is established (reaction rate is infinite).
2.2.1 Ionization equilibrium of hydrogen atoms.
2.2.2 Dissociation equilibrium of hydrogen molecules.
2.3 Electrical neutrality.
2.4 Equation of state.
2.5 Boltzmann distribution law between excited levels.
In general, the ionization equilibrium for particle A is described as the Saha equation.
[Formula 1]
The dissociation equilibrium between the molecule AB and the particles A and B is known as the Guldberg-Waage equation.
[Formula 2]
N is the particle density, k B is the Boltzmann constant, h is the Planck constant, g is the internal state sum, E ion is the ionization energy, and E dis is the dissociation energy.
The electrical neutral condition and the equation of state are described as follows.
[Formula 3]
[Formula 4]
Or N H2, in the electron temperature T at the 4 formula N H, N H +, can be calculated the density of 4 particles N e. The particle composition calculated from these equations is shown in FIG. The horizontal axis represents the electron temperature T [K], and the vertical axis represents the particle density N [m −3 ].
図２の結果より、水素プラズマの電子温度が高くなると水素粒子密度（ＮＨ２）が低下し、約６，０００Ｋ以上になると、水素ラジカルの一種である水素原子（ＮＨ）や、水素イオン（ＮＨ＋）もしくは電子（Ｎｅ）として存在する。１０，０００Ｋ程度以上の電子温度領域では、水素は分子として存在することができず、ラジカルの一種である水素原子Ｈや水素イオンＨ＋として存在していることがわかる。また、１５，０００Ｋ程度以上の電子温度領域では、水素原子（ＮＨ）が次第に減少し、水素イオン（ＮＨ＋）もしくは電子（Ｎｅ）として存在する。このことは、１５，０００Ｋ以下の電子温度領域では、水素ラジカルの発生量が多い状態となり、これらの粒子は反応性が高いため水素還元反応に有効に作用すると考えられる。 From the results of FIG. 2, the hydrogen particle density (N H2 ) decreases as the electron temperature of the hydrogen plasma increases, and when it reaches about 6,000 K or higher, hydrogen atoms (N H ), which are a kind of hydrogen radicals, and hydrogen ions ( N H + ) or electrons (Ne). It can be seen that in the electron temperature range of about 10,000 K or more, hydrogen cannot exist as a molecule but exists as a hydrogen atom H or a hydrogen ion H + which is a kind of radical. Further, in an electron temperature range of about 15,000 K or more, hydrogen atoms (N H ) gradually decrease and exist as hydrogen ions (N H + ) or electrons (Ne). This is considered that in the electron temperature region of 15,000 K or less, a large amount of hydrogen radicals are generated, and these particles are highly reactive and thus effectively act on the hydrogen reduction reaction.
全粒子中における各粒子の存在比率を表１に示す。
［二線強度比法］
次に、水素プラズマの特性や有効性を検討するために電子温度に着目し実験した結果を示す。
一般にプラズマの測定手法としては磁気プローブ計測、静電プローブ計測、干渉法、レーザ散乱計測、発光分光計測、レーザ誘起蛍光法、ラマン分光法、粒子計測法など様々な手法が挙げられる。水素プラズマは、発生の位置再現性に乏しい。そのため、電子温度の測定にあたっては電子温度の２次元分布を単一測定で取得する必要がある。そこで、発光分光計測の一種である二線強度比法（＊）を採用し、各線強度の２次元分布を同時測定した。
＊W.L.Wiese and J.R.Fuhr “Accurate atomic transition probabilities for hydrogen, helium, and lithium”, J.Phys.Chem.Ref.Data,Vol.38,No.3,pp.565-719(2009)
[Two wire intensity ratio method]
Next, the results of experiments focusing on the electron temperature in order to study the characteristics and effectiveness of hydrogen plasma are shown.
In general, plasma measurement techniques include various techniques such as magnetic probe measurement, electrostatic probe measurement, interferometry, laser scattering measurement, emission spectroscopy measurement, laser-induced fluorescence method, Raman spectroscopy, and particle measurement method. Hydrogen plasma has poor position reproducibility. Therefore, when measuring the electron temperature, it is necessary to obtain a two-dimensional distribution of the electron temperature by a single measurement. Therefore, the two-line intensity ratio method (*), which is a kind of emission spectroscopic measurement, was employed to simultaneously measure the two-dimensional distribution of each line intensity.
* WLWiese and JRFuhr “Accurate atomic transition probabilities for hydrogen, helium, and lithium”, J.Phys.Chem.Ref.Data, Vol.38, No.3, pp.565-719 (2009)
二線強度比法は、準位ｉからｊへの遷移及びｋからｌへの遷移により放出される発光のスペクトルを利用して電子温度を算出する手法である。発光のスペクトル強度Ｉｉｊ，Ｉｋｌは次のように表される。
［式５］
［式６］
ｖは観測スペクトルの周波数、Ａはエネルギー準位遷移の確率、Ｎは粒子密度である。熱平衡状態では、励起準位にある粒子の密度はボルツマン分布で与えられる。したがって２種のスペクトルの粒子密度比は式（７）のように表される。
［式７］
ｇはその準位の縮退度を表している。式（５）（６）（７）より発光強度比は式（８）で表わされる。式（８）から電子温度Ｔを逆算すると式（９）で表わされる関係式が得られる。
［式８］
［式９］
The two-line intensity ratio method is a method of calculating an electron temperature using a spectrum of light emission emitted by a transition from a level i to j and a transition from k to l. The emission spectral intensities I ij and I kl are expressed as follows.
[Formula 5]
[Formula 6]
v is the frequency of the observed spectrum, A is the probability of energy level transition, and N is the particle density. In the thermal equilibrium state, the density of the particles in the excited level is given by a Boltzmann distribution. Therefore, the particle density ratio of the two types of spectra is expressed as in Equation (7).
[Formula 7]
g represents the degree of degeneracy of the level. From formulas (5), (6), and (7), the emission intensity ratio is represented by formula (8). When the electron temperature T is calculated backward from Equation (8), the relational expression represented by Equation (9) is obtained.
[Formula 8]
[Formula 9]
本実験では、水素プラズマから発せられるバルマー系列線であるＨα線（６５６ｎｍ）とＨβ線（４８６ｎｍ）を利用する。Ｈα線は量子数３から量子数２への遷移、Ｈβ線は量子数４から量子数２への遷移である。水素のエネルギー準位や縮退度等から算出した電子温度ＴとＩα／Ｉβの関係は図３のようになる。１０，０００Ｋ程度では発光強度に対し電子温度はゆるやかな変化を示す。しかし２０，０００Ｋを越えるような比較的高い電子温度の場合には、発光強度のわずかな変化に対して電子温度が急激に変化するため、発光強度の測定上の誤差の影響が大きくなる。 In this experiment, H α rays (656 nm) and H β rays (486 nm), which are Ballmer series lines emitted from hydrogen plasma, are used. The H α ray is a transition from the quantum number 3 to the quantum number 2, and the H β ray is a transition from the quantum number 4 to the quantum number 2. FIG. 3 shows the relationship between the electron temperature T calculated from the energy level of hydrogen, the degree of degeneracy, and the like, and I α / I β . At about 10,000 K, the electron temperature shows a gradual change with respect to the emission intensity. However, in the case of a relatively high electron temperature exceeding 20,000 K, the electron temperature changes abruptly with respect to a slight change in the emission intensity, so that the influence of errors in the measurement of the emission intensity becomes large.
［シングルモードマイクロ波発生装置による実験］
次に、マイクロ波照射時の発光を撮影した結果を示す。
実験に用いたシングルモードマイクロ波発生装置図を図４に示す。該実験装置は、処理溶液を設置するシングルモードマイクロ波発生装置と、反応時の発光を撮影するためのレンズ部の２つに分けられる。これらの詳細を順に述べる。
実際の脱塩素化反応においては、水素供与体、脱塩素剤触媒及びＰＣＢを用いる。図１に示すように、本実験においては、水素供与体兼希釈用液としてイソプロピルアルコール（ＩＰＡ）、脱塩素剤として水酸化カリウム（ＫＯＨ）、触媒としてはパラジウムを粒状活性炭に担持させたもの（Ｐｄ／Ｃ）を使用する。しかし、濃度の観点から脱塩素剤ＫＯＨ及びＰＣＢが水素プラズマに及ぼす影響は小さいと考え、これらを使用しないこととした。
実験ではＩＰＡと絶縁油（炭化水素油）を混合し、溶液を調製した。そしてこの混合溶液１０ｍｌ、Ｐｄ／Ｃ触媒５ｇを石英試験管に封入した。混合溶液の比率はＩＰＡ：Ｏｉｌ＝５０：５０，７０：３０，９０：１０の三種類とした。
シングルモードマイクロ波発生装置からこれらの溶液へおよそ３００Ｗ、２．４５ＧＨｚのＭＷを照射し、溶液内の微小バブル中に水素プラズマを発生させる。ここで、マイクロ波出力は任意に調整可能である。溶液温度は５０℃から６０℃、圧力は大気圧とし、測定を行った。温度が一定でないのはＭＷによる温度上昇が急速で、温度制御が困難であったためである。
[Experiments with a single-mode microwave generator]
Next, the result of photographing light emission during microwave irradiation is shown.
FIG. 4 shows a diagram of a single mode microwave generator used in the experiment. The experimental apparatus can be divided into two parts: a single mode microwave generator in which a processing solution is installed, and a lens unit for photographing light emission during reaction. These details will be described in turn.
In the actual dechlorination reaction, a hydrogen donor, a dechlorinating agent catalyst and PCB are used. As shown in FIG. 1, in this experiment, isopropyl alcohol (IPA) as a hydrogen donor / dilution liquid, potassium hydroxide (KOH) as a dechlorinating agent, and palladium as a catalyst are supported on granular activated carbon ( Pd / C) is used. However, the dechlorination agents KOH and PCB are considered to have little influence on the hydrogen plasma from the viewpoint of concentration, and these were not used.
In the experiment, IPA and insulating oil (hydrocarbon oil) were mixed to prepare a solution. Then, 10 ml of this mixed solution and 5 g of Pd / C catalyst were sealed in a quartz test tube. The ratio of the mixed solution was IPA: Oil = 50: 50, 70:30, 90:10.
These solutions are irradiated with about 300 W and 2.45 GHz MW from a single mode microwave generator to generate hydrogen plasma in microbubbles in the solution. Here, the microwave output can be arbitrarily adjusted. The measurement was performed at a solution temperature of 50 ° C. to 60 ° C. and a pressure of atmospheric pressure. The reason why the temperature is not constant is that the temperature rise due to MW is rapid and it is difficult to control the temperature.
次にレンズ部について述べる。シングルモードマイクロ波発生装置側から順にビームスプリッタモジュール、イメージインテンシファイア（以下Ｉ．Ｉ．）、インテンシファイドチャージカップルドデバイスカメラ（以下ＩＣＣＤカメラ）により構成される。ビームスプリッタモジュール内部にはダイクロイックミラー及び干渉フィルタを導入した。そのためＩ．Ｉ．側の出口では、水素プラズマから放射されたＨα線とＨβ線の２波長が選択的に出力される。本モジュールでは、水素プラズマのＨα線とＨβ線の２次元的な発光像が、一つのカメラのＣＣＤチップ面上に半面ずつ結像する構成になっている。このようにして得られた各波長のスペクトル間で強度比をとることにより電子温度を求める。撮影はＩＣＣＤカメラのゲート時間を３０ｍｓ、撮影間隔を２ｓに設定した。そして、２波長のスペクトル１０回連続で撮影し、この試行を複数回繰り返した。 Next, the lens unit will be described. It is composed of a beam splitter module, an image intensifier (hereinafter referred to as II), and an intensified charge coupled device camera (hereinafter referred to as ICCD camera) in order from the single mode microwave generator side. A dichroic mirror and an interference filter were introduced inside the beam splitter module. Therefore I. I. At the outlet on the side, two wavelengths of Hα rays and Hβ rays radiated from the hydrogen plasma are selectively output. In this module, a two-dimensional light emission image of Hα rays and Hβ rays of hydrogen plasma is formed on each CCD chip surface of one camera half by side. The electron temperature is obtained by taking the intensity ratio between the spectra of the respective wavelengths thus obtained. For shooting, the gate time of the ICCD camera was set to 30 ms, and the shooting interval was set to 2 s. The two-wavelength spectrum was continuously photographed 10 times, and this trial was repeated a plurality of times.
［実験結果］
溶液組成が５０：５０の溶液に２９０ＷのＭＷを照射した際にＩＣＣＤカメラにより撮影された発光画像を図５に示す。
図５より、先述のレンズ系を用いることにより、２波長のスペクトルの２次元分布が一つのカメラで測定できている。
溶液組成がＩＰＡ：Ｏｉｌ＝５０：５０、マイクロ波発生装置の出力電力を２９０Ｗとした場合の電子温度をヒストグラム形式で図６に示す。図６では横軸に電子温度Ｔ［Ｋ］をとり、縦軸に発生比率をとっている。図６の電子温度分布は５，０００Ｋから１５，０００Ｋの付近にピークを持ち、凸形の形状を持つ。この形状は溶液比率やマイクロ波出力に依存していなかった。
[Experimental result]
FIG. 5 shows a light emission image taken by an ICCD camera when 290 W MW was irradiated to a solution having a solution composition of 50:50.
From FIG. 5, by using the lens system described above, the two-dimensional distribution of the spectrum of two wavelengths can be measured with one camera.
FIG. 6 shows the electron temperature in a histogram format when the solution composition is IPA: Oil = 50: 50 and the output power of the microwave generator is 290 W. In FIG. 6, the horizontal axis represents the electron temperature T [K], and the vertical axis represents the generation ratio. The electron temperature distribution in FIG. 6 has a peak in the vicinity of 5,000K to 15,000K and has a convex shape. This shape did not depend on the solution ratio or microwave output.
様々なマイクロ波出力に対する電子温度の測定結果を図７に示す。図７中では横軸にマイクロ波出力値［Ｗ］、縦軸に電子温度［Ｋ］をとっている。＋点は多数回測定した電子温度の平均値を示している。そして○点は測定の失敗を考慮し、測定値の上下１割をカットした場合の範囲を示している。
溶液がＩＰＡ：Ｏｉｌ＝５０：５０の場合、出力約１７０Ｗ以上では、電子温度はマイクロ波出力に対して、わずかに正の相関を示しておりその値は８，６００Ｋ程度であった。ＩＰＡ：Ｏｉｌ＝７０：３０の場合、出力約１７０Ｗ以上ではマイクロ波出力に対してわずかに負の相関を示している。この場合、電子温度は１０，０００Ｋ程度であった。ＩＰＡ：Ｏｉｌ＝９０：１０の溶液では発光が微弱なため、マイクロ波出力が２７０Ｗの場合のみ電子温度は測定可能であった。その時の温度は９，４００Ｋ程度であった。これらの電子温度領域では図２で示したよう、活性種である水素原子Ｈや水素イオンＨ＋が多量に存在していると考えられる。
FIG. 7 shows the measurement results of the electron temperature with respect to various microwave outputs. In FIG. 7, the horizontal axis represents the microwave output value [W], and the vertical axis represents the electron temperature [K]. The + point indicates the average value of the electron temperature measured many times. The circles indicate the range when the upper and lower 10% of the measured values are cut in consideration of measurement failure.
When the solution was IPA: Oil = 50: 50, when the output was about 170 W or more, the electron temperature showed a slight positive correlation with the microwave output, and the value was about 8,600K. When IPA: Oil = 70: 30, an output of about 170 W or more shows a slightly negative correlation with the microwave output. In this case, the electron temperature was about 10,000K. In the solution of IPA: Oil = 90: 10, since the light emission was weak, the electron temperature was measurable only when the microwave output was 270 W. The temperature at that time was about 9,400K. In these electron temperature regions, it is considered that a large amount of hydrogen atoms H and hydrogen ions H + which are active species are present as shown in FIG.
図７の結果より、マイクロ波出力１７０Ｗ以上の領域では、水素プラズマの電子温度とマイクロ波出力とが正の相関あるいは負の相関を示すことから、ＩＰＡ：Ｏｉｌの比を変えることで、水素プラズマの電子温度ひいては水素ラジカル等の発生量の制御が可能になることがわかる。また、ＩＰＡ：Ｏｉｌの比が一定の場合は、マイクロ波照射強度を変えることで、水素プラズマの電子温度ひいては水素ラジカル等の発生量の制御が可能になることがわかる。 From the result of FIG. 7, in the region where the microwave output is 170 W or more, the electron temperature of the hydrogen plasma and the microwave output show a positive correlation or a negative correlation. Therefore, by changing the IPA: Oil ratio, the hydrogen plasma It can be seen that it is possible to control the generation temperature of hydrogen radicals and the like, and the generation amount of hydrogen radicals and the like. It can also be seen that when the ratio of IPA: Oil is constant, the electron temperature of the hydrogen plasma and thus the generation amount of hydrogen radicals and the like can be controlled by changing the microwave irradiation intensity.
ＩＰＡ：Ｏｉｌの比を変えた３つの系における、マイクロ波出力と発光頻度の関係を図８に示す。横軸はマイクロ波出力値［Ｗ］、縦軸は１００枚の写真中に観測された発光点数を表している。マイクロ波出力値と発光頻度には明らかな正の相関があり、高出力時には水素の気泡が多く発生していることが推察される。
溶液組成による影響としてはＩＰＡの比率が少ないほど発光頻度が大きいということがわかる。グラフの形はどれもほぼ同型であり、組成による著しい影響はみられなかった。図８において、マイクロ波出力値２５０Ｗの時の発光イベント数は、ＩＰＡ：Ｏｉｌ＝５０：５０では約２８０、７０：３０では約１８０であった。ＩＰＡとＯｉｌの混合溶液１０ｍｌ中のＩＰＡの比率が高いほどＩＰＡ分子数が多くなるので、ＩＰＡ分子数が１．４倍になれば分子１個当たりが受けるマイクロ波光子数（フォトン数）は１／１．４倍になるが、測定発光イベント数は１８０／２８０＝１／１．５６であり、ＩＰＡの絶対量がマイクロ波による発光イベント数に影響することが考察された。このことから、被処理物質と水素供与体を含有する液状物を触媒を充填したカラムに流通させながらマイクロ波を照射する方法は、水素ラジカルを多く発生させることができる効率的な方法であると言える。
FIG. 8 shows the relationship between the microwave output and the light emission frequency in three systems with different IPA: Oil ratios. The horizontal axis represents the microwave output value [W], and the vertical axis represents the number of emission points observed in 100 photographs. There is a clear positive correlation between the microwave output value and the emission frequency, and it is assumed that many hydrogen bubbles are generated at high output.
As the influence of the solution composition, it can be seen that the smaller the IPA ratio, the greater the emission frequency. All of the graph shapes were almost the same type, and no significant effect of the composition was observed. In FIG. 8, the number of light emission events when the microwave output value is 250 W was about 280 when IPA: Oil = 50: 50, and about 180 when 70:30. As the IPA ratio in 10 ml of a mixed solution of IPA and Oil increases, the number of IPA molecules increases. Therefore, when the number of IPA molecules increases by 1.4 times, the number of microwave photons (number of photons) received per molecule is 1. However, the number of measured light emission events is 180/280 = 1 / 1.56, and it was considered that the absolute amount of IPA affects the number of light emission events caused by microwaves. From this, the method of irradiating microwaves while circulating a liquid material containing a substance to be treated and a hydrogen donor through a column packed with a catalyst is an efficient method capable of generating a large amount of hydrogen radicals. I can say that.
［ＰＣＢ脱塩素化装置による実験］
図４の簡易的マイクロ波発生装置を、現在、廃電気機器の処理に利用している装置と同型のものに変更した。実験装置図を図９に示す。
上記のシングルモードマイクロ波発生装置と同様、実験系はマイクロ波発生装置とレンズ部の２つに分類できる。レンズ部は前記試験と同様である。
溶液組成は発光現象が最も発生しやすい条件であるＩＰＡ：Ｏｉｌ＝５０：５０とし、混合溶液１６Ｌ，Ｐｄ／Ｃ触媒２ｋｇを円筒型のＰＣＢ脱塩素化装置に封入する。その溶液に対し、マイクロ波発生装置から最大９００ＷでＭＷを照射する。ＭＷの出力は任意に調整が可能である。
またＰＣＢ脱塩素化装置では溶液内部の温度ムラを防ぐために、溶液を装置の内外へと絶えず循環させている。また装置内での発火を防ぐため窒素ガスを還流させ、酸素濃度を低く抑えている。
溶液温度は５５℃から６０℃、圧力は大気圧とし、測定を行った。温度が一定ではないのはＭＷによる温度上昇が急速で温度制御が困難であったためである。
撮影はＩＣＣＤカメラのゲート時間を１００ｍｓ、各撮影間隔を２ｓに設定した。そして、２波長のスペクトルを１００回連続で撮影し、この試行を複数回繰り返した。
[Experiment with PCB dechlorination equipment]
The simple microwave generator shown in FIG. 4 is changed to the same type as that currently used for processing waste electrical equipment. An experimental apparatus diagram is shown in FIG.
Similar to the single mode microwave generator described above, the experimental system can be classified into a microwave generator and a lens unit. The lens part is the same as in the above test.
The solution composition is IPA: Oil = 50: 50, which is the most likely condition for the light emission phenomenon, and 16 L of mixed solution and 2 kg of Pd / C catalyst are sealed in a cylindrical PCB dechlorination apparatus. The solution is irradiated with MW at a maximum of 900 W from the microwave generator. The output of MW can be adjusted arbitrarily.
Further, in the PCB dechlorination apparatus, the solution is circulated constantly inside and outside the apparatus in order to prevent temperature unevenness inside the solution. In order to prevent ignition in the apparatus, nitrogen gas is refluxed to keep the oxygen concentration low.
The measurement was performed at a solution temperature of 55 ° C. to 60 ° C. and a pressure of atmospheric pressure. The reason why the temperature is not constant is that the temperature rise due to MW is rapid and temperature control is difficult.
For shooting, the gate time of the ICCD camera was set to 100 ms, and each shooting interval was set to 2 s. Then, a spectrum of two wavelengths was photographed 100 times continuously, and this trial was repeated a plurality of times.
［実験結果］
上記実験系にて撮影した発光画像を図１０に示す。これは９００Ｗの出力値で照射した際の発光の様子である。シングルモードマイクロ波発生装置試験と左右の波長が逆転しているが、これはレンズを１８０°回転させているためである。この画像から実際のＰＣＢ脱塩素化装置においても水素プラズマが発生していることが確認できる。照射強度が７３５Ｗの場合のヒストグラムを電子温度分布の一例として図１１に示す。電子温度分布はシングルモードマイクロ波発生装置試験と同様、５，０００−１５，０００Ｋ程度にピークを持つ。
シングルモードマイクロ波発生装置試験と同様、発光強度から算出した電子温度を図１２に示す。電子温度は多少変動しながらもおおよそ９，０００Ｋ程度である。この温度はシングルモードマイクロ波発生装置試験とほぼ同等の温度であり、電子温度は溶液タンクのサイズや触媒の量と無関係といえる。
発光頻度のマイクロ波出力に対するグラフを図１３に示す。発光頻度はマイクロ波出力と正の相関関係にある。しかしながら、その発光頻度は１から１０程度の間であり、シングルモードマイクロ波発生装置試験と比較して著しく減少している。そのため実際のＰＣＢ脱塩素化装置では水素があまり発生しておらず、ＰＣＢ分解効率が低下している可能性も考えられる。
[Experimental result]
FIG. 10 shows a luminescence image taken in the experimental system. This is the state of light emission when irradiated with an output value of 900 W. The left and right wavelengths are reversed from the single mode microwave generator test because the lens is rotated 180 °. From this image, it can be confirmed that hydrogen plasma is also generated in an actual PCB dechlorination apparatus. A histogram when the irradiation intensity is 735 W is shown in FIG. 11 as an example of the electron temperature distribution. Similar to the single mode microwave generator test, the electron temperature distribution has a peak at about 5,000 to 15,000K.
As in the single mode microwave generator test, the electron temperature calculated from the emission intensity is shown in FIG. The electron temperature is about 9,000 K with some fluctuations. This temperature is almost the same as the single mode microwave generator test, and the electron temperature is independent of the size of the solution tank and the amount of catalyst.
A graph of the emission frequency with respect to the microwave output is shown in FIG. The emission frequency is positively correlated with the microwave output. However, the emission frequency is between about 1 and 10, which is significantly reduced compared to the single mode microwave generator test. Therefore, there is a possibility that the actual PCB dechlorination apparatus does not generate much hydrogen and the PCB decomposition efficiency is lowered.
以上説明したように、本発明ではマイクロ波照射ＰＣＢ脱塩素化反応時に発生する水素プラズマの特性と有効性を検討するためにその電子温度に着目した。水素プラズマ中で水素がどのような状態で存在しているか検討するために、気泡の構成粒子が水素分子、原子、イオン、及び電子のみであるとし、さらに局所熱平衡性を仮定し計算を行った。その結果、電子温度として想定される４，０００Ｋから１５，０００Ｋ程度では水素は解離してラジカルもしくは電離して正イオンとして存在していることがわかった。
簡易的なマイクロ波発生装置にて実験を行ったところ、電子温度は溶液組成によって異なり、出力１７０Ｗ以上では、ＩＰＡ：Ｏｉｌ＝５０：５０の場合およそ８，６００Ｋ，７０：３０の場合およそ１０，０００Ｋと、ＩＰＡが多いほうがより電子温度が高くなっていた。これらの温度では水素ラジカル等が大量に発生していると考えられる。
As described above, the present invention focuses on the electron temperature in order to study the characteristics and effectiveness of the hydrogen plasma generated during the microwave irradiation PCB dechlorination reaction. In order to investigate how hydrogen is present in the hydrogen plasma, it was assumed that the constituent particles of the bubble were only hydrogen molecules, atoms, ions, and electrons, and further calculations were performed assuming local thermal equilibrium. . As a result, it was found that hydrogen was dissociated and radicals or ionized to exist as positive ions at an electron temperature of about 4,000 K to 15,000 K.
When an experiment was conducted using a simple microwave generator, the electron temperature varied depending on the solution composition, and when the output was 170 W or more, approximately 8,600 K when IPA: Oil = 50: 50, approximately 10, when 70:30. The higher the IPA, the higher the electron temperature was 000K. It is considered that a large amount of hydrogen radicals are generated at these temperatures.
発光頻度は溶液組成によって異なり、ＩＰＡが少ないほど発光頻度が多くなっていた。また、発光頻度はマイクロ波出力値が大きいほど高くなっていたため、水素ラジカルの生成量も増加していたと考えられる。
実際のＰＣＢ脱塩素化装置において実験を行った際にも水素プラズマが確認され、その電子温度は９，０００Ｋ程度であった。これはシングルモードマイクロ波発生装置と同程度である。また電子温度分布についても類似した形状を示すことが確認された。
The emission frequency varies depending on the solution composition, and the lower the IPA, the higher the emission frequency. Further, since the emission frequency was higher as the microwave output value was larger, it is considered that the amount of hydrogen radicals generated was also increased.
Hydrogen plasma was also confirmed when an experiment was performed in an actual PCB dechlorination apparatus, and the electron temperature was about 9,000K. This is comparable to a single mode microwave generator. It was also confirmed that the electron temperature distribution showed a similar shape.
本発明に係る水素プラズマの発生方法は、ＰＣＢ脱塩素化反応の促進に寄与するので、ＰＣＢ、ＰＣＢの模擬物質であるトリクロロベンゼン、ダイオキシン類の脱塩素化の他、重質油の軽質化、二酸化炭素の還元固定、劣化潤滑油の還元再生、医薬品合成等における様々な還元反応に利用できる。 The method for generating hydrogen plasma according to the present invention contributes to the promotion of PCB dechlorination reaction. Therefore, in addition to dechlorination of PCBs, trichlorobenzene and dioxins which are simulated substances of PCB, lightening of heavy oil, It can be used for various reduction reactions in carbon dioxide reduction fixation, reduction regeneration of deteriorated lubricating oil, pharmaceutical synthesis and the like.
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