JP2000136151A - Production of dehalogenated compound - Google Patents
Production of dehalogenated compoundInfo
- Publication number
- JP2000136151A JP2000136151A JP10309968A JP30996898A JP2000136151A JP 2000136151 A JP2000136151 A JP 2000136151A JP 10309968 A JP10309968 A JP 10309968A JP 30996898 A JP30996898 A JP 30996898A JP 2000136151 A JP2000136151 A JP 2000136151A
- Authority
- JP
- Japan
- Prior art keywords
- halide
- compound
- photocatalyst
- dehalogenated
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 claims abstract description 55
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 21
- 229920000265 Polyparaphenylene Polymers 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- -1 polyparaphenylene Polymers 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 40
- 239000010419 fine particle Substances 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 238000007540 photo-reduction reaction Methods 0.000 abstract description 6
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 230000001939 inductive effect Effects 0.000 abstract 1
- 238000012937 correction Methods 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 20
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 229910052984 zinc sulfide Inorganic materials 0.000 description 14
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000005083 Zinc sulfide Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000006298 dechlorination reaction Methods 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002367 halogens Chemical class 0.000 description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 9
- 238000005695 dehalogenation reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 150000001555 benzenes Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000008422 chlorobenzenes Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- ZQTOAGFBKREYIO-UHFFFAOYSA-N 2-(4-hydroxyphenyl)cyclohexa-2,5-diene-1,4-dione Chemical compound C1=CC(O)=CC=C1C1=CC(=O)C=CC1=O ZQTOAGFBKREYIO-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- GPLIMIJPIZGPIF-UHFFFAOYSA-N 2-hydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C=CC1=O GPLIMIJPIZGPIF-UHFFFAOYSA-N 0.000 description 2
- OPAHIYVGXFZZJH-UHFFFAOYSA-N 4-chloro-2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC(Cl)=CC=C1O OPAHIYVGXFZZJH-UHFFFAOYSA-N 0.000 description 2
- WWOBYPKUYODHDG-UHFFFAOYSA-N 4-chlorocatechol Chemical compound OC1=CC=C(Cl)C=C1O WWOBYPKUYODHDG-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- JFNWQOHVPQHYQL-UHFFFAOYSA-N 2-(4-hydroxyphenyl)benzene-1,4-diol Chemical group C1=CC(O)=CC=C1C1=CC(O)=CC=C1O JFNWQOHVPQHYQL-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- ZPHQBFRCXUIIAZ-UHFFFAOYSA-N benzene;hydrochloride Chemical class Cl.C1=CC=CC=C1 ZPHQBFRCXUIIAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052981 lead sulfide Inorganic materials 0.000 description 1
- 229940056932 lead sulfide Drugs 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fire-Extinguishing Compositions (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光還元的脱ハロゲ
ン化反応による含ハロゲン化合物の解毒方法に関する。[0001] The present invention relates to a method for detoxifying a halogen-containing compound by a photoreductive dehalogenation reaction.
【０００２】[0002]
【従来の技術】含ハロゲン化合物の解毒を光エネルギー
を用いて行う方法は、従来、酸化チタンを用いて検討さ
れてきた。この手法では、微量の塩化ベンゼン、塩化ア
ルキル、クロロフェノール等を含む水中に酸化チタン粉
末を懸濁し、酸素の存在下で光照射すると、上記化合物
が分解され、ＣＯ2 と水及び塩酸となるものである。2. Description of the Related Art A method of detoxifying a halogen-containing compound using light energy has been conventionally studied using titanium oxide. In this method, titanium oxide powder is suspended in water containing trace amounts of benzene chloride, alkyl chloride, chlorophenol, and the like, and when irradiated with light in the presence of oxygen, the above compounds are decomposed into CO 2 , water, and hydrochloric acid. It is.
【０００３】この手法では、光照射によって酸化チタン
粒子中に励起電子と正孔が生成し、含ハロゲン化合物の
酸化反応は、正孔による化合物の直接酸化反応、及び水
分子を正孔が酸化することによって生じたヒドロキシル
ラジカルが化合物を攻撃することによって起こる。[0003] In this method, excited electrons and holes are generated in titanium oxide particles by light irradiation, and the oxidation reaction of a halogen-containing compound involves direct oxidation of the compound by holes and oxidation of water molecules by holes. The resulting hydroxyl radicals attack the compound.
【０００４】しかしながら、ハロゲン原子を多く含む分
子ほど酸化反応には耐性が強く、酸化反応が起こりにく
いという問題があり、ポリ塩化ビフェニール（ＰＣＢ）
等のポリハロゲン化物には活性が低いという問題があっ
た。さらに、酸化反応が不完全な場合、酸化過程で生じ
る中間体はしばしば最初の化合物より毒性が高い、すな
わち、有毒な反応中間体が生じるという問題がある。However, there is a problem that molecules containing more halogen atoms are more resistant to the oxidation reaction and the oxidation reaction is less likely to occur, and polychlorinated biphenyl (PCB)
The polyhalide has a problem of low activity. Furthermore, if the oxidation reaction is incomplete, the intermediate formed in the oxidation process is often more toxic than the first compound, ie, a toxic reaction intermediate is formed.
【０００５】また、光エネルギーを用いて、ポリハロゲ
ン化合物を酸化でなく、還元反応により、より毒性の低
い化合物に転換する方法が知られている（J. Phys. Che
m. 1996, 100, 2161〜2169、Environ. Sci. Technol. 1
995, 29, 1646 〜1654及びEnviron. Sci. Technol. 199
6, 30, 2547 〜2555参照) 。Also, a method is known in which light energy is used to convert a polyhalogen compound into a less toxic compound by a reduction reaction instead of oxidation (J. Phys. Che).
m. 1996, 100, 2161-2169, Environ. Sci. Technol. 1
995, 29, 1646-1654 and Environ. Sci. Technol. 199
6, 30, 2547-2555).
【０００６】[0006]
【発明が解決しようとする課題】しかし、本発明者は、
このような還元反応では、硫化カドミウムや酸化チタン
の還元力が弱く、最終的に、ポリハロゲン化合物を燃焼
処理になんら支障のない有機化合物まで導くには、脱ハ
ロゲン化反応が十分でないことを突き止めた。However, the present inventor has
In such a reduction reaction, the reduction power of cadmium sulfide and titanium oxide is weak, and it is found that the dehalogenation reaction is not enough to eventually lead the polyhalogen compound to an organic compound that does not hinder the combustion treatment. Was.
【０００７】また、酸化チタンの吸収する光の波長は４
００nm以下の領域であり、ポリハロゲン化合物を光還元
によって脱ハロゲン化しようとする場合、太陽光スペク
トルの短波長の１部分しか用いることができない。The wavelength of light absorbed by titanium oxide is 4
When the polyhalogen compound is to be dehalogenated by photoreduction, only a part of the short wavelength of the solar spectrum can be used.
【０００８】なお、Theoretical and Experimental Che
mistry, 30(1994), 30〜33には、エタノール中の硫化カ
ドミウムを用いて、光還元反応によってヘキサクロロベ
ンゼンを脱ハロゲン化することが記載されている。しか
し、この文献に記載された硫化カドミウムは、ハロゲン
化物の脱ハロゲン化に際して、光触媒として機能してい
ないことは明らかである。Theoretical and Experimental Che
Mistry, 30 (1994), 30-33, describes the use of cadmium sulfide in ethanol to dehalogenate hexachlorobenzene by a photoreduction reaction. However, it is clear that cadmium sulfide described in this document does not function as a photocatalyst in dehalogenating halides.
【０００９】その理由は、通常の硫化カドミウム（マイ
クロサイズ）の場合、伝導帯の下端は、標準電極（ＳＣ
Ｅ）に対して、-0.8V 〜-1.3V と見積もられている（A.
J.Nozik and R. Memming, J. Phys. Chem., 100, 1306
1〜13078(1996) 参照）。しかし、ヘキサクロロベンゼ
ン、ペンタクロロベンゼン、テトラクロロベンゼン、ト
リクロロベンゼン、ジクロロベンゼン及びモノクロロベ
ンゼンの還元電位は、それぞれ、-1.32 、-1.57 、-1.7
6(1,2,3,4-クロロ体) 、-1.96(1,2,3-クロロ体) 、-2.2
2(1,2-クロロ体) 及び-2.44Vである（A. J. Bard and
H. Lund, Encyclopedia of Electrochemistry of the E
lements, Organic Section, Vol.XIV, Marcel Dekker,
New York, 1980, pp.181 〜185 参照）。したがって、
電気化学的には、硫化カドミウムは光触媒として機能せ
ず、クロロベンゼン誘導体の脱ハロゲン化及び水素化反
応は起こらない。The reason is that in the case of ordinary cadmium sulfide (micro size), the lower end of the conduction band is connected to the standard electrode (SC).
E), it is estimated to be -0.8V to -1.3V (A.
J. Nozik and R. Memming, J. Phys. Chem., 100, 1306
1-113078 (1996)). However, the reduction potentials of hexachlorobenzene, pentachlorobenzene, tetrachlorobenzene, trichlorobenzene, dichlorobenzene, and monochlorobenzene were -1.32, -1.57, and -1.7, respectively.
6 (1,2,3,4-chloro form), -1.96 (1,2,3-chloro form), -2.2
2 (1,2-chloro form) and -2.44 V (AJ Bard and
H. Lund, Encyclopedia of Electrochemistry of the E
lements, Organic Section, Vol.XIV, Marcel Dekker,
New York, 1980, pp. 181-185). Therefore,
Electrochemically, cadmium sulfide does not function as a photocatalyst, and no dehalogenation or hydrogenation reaction of the chlorobenzene derivative occurs.
【００１０】また、硫化カドミウムの価電子帯の上端
は、標準電極（ＳＣＥ）に対して、1.2V程度と見積もら
れている（上記 A. J. Nozik and R. Memming, J. Phy
s. Chem., 100, 13061 〜13078(1996) 参照）。ところ
で、エタノールの酸化電位は、2.7Vである（A. J. Bard
and H. Lund, Encyclopedia of Electrochemistry of
the Elements, Organic Section, Vol.XI, Marcel Dekk
er, New York, 1980, p.182 参照）。したがって、電気
化学的には、硫化カドミウムは光触媒として機能せず、
エタノールの酸化反応は起こらず、エタノールを電子源
とすることは不可能である。The upper end of the valence band of cadmium sulfide is estimated to be about 1.2 V with respect to the standard electrode (SCE) (see AJ Nozik and R. Memming, J. Phy.
s. Chem., 100, 13061-13078 (1996)). By the way, the oxidation potential of ethanol is 2.7V (AJ Bard
and H. Lund, Encyclopedia of Electrochemistry of
the Elements, Organic Section, Vol.XI, Marcel Dekk
er, New York, 1980, p.182). Therefore, electrochemically, cadmium sulfide does not function as a photocatalyst,
No oxidation reaction of ethanol occurs, and it is impossible to use ethanol as an electron source.
【００１１】さらに、光触媒は、酸素が存在する場合、
酸素が電子を伝導帯から優先的に奪うため、還元反応を
行うことはできない。しかも、このような反応系に、硫
化カドミウムを用いる場合、硫化カドミウムが光溶解す
ることが知られている。[0011] Furthermore, the photocatalyst, when oxygen is present,
Oxygen preferentially removes electrons from the conduction band, so that a reduction reaction cannot be performed. Moreover, when cadmium sulfide is used in such a reaction system, it is known that cadmium sulfide is photo-dissolved.
【００１２】このように、Theoretical and Experiment
al Chemistry, 30(1994), 30〜33に記載された硫化カド
ミウムは、光触媒として機能し得ないので、この文献に
記載されたようにして硫化カドミウムを用いてエタノー
ル中でヘキサクロロベンゼンを脱ハロゲン化すること
は、到底不可能である。Thus, Theoretical and Experiment
Cadmium sulfide described in Al Chemistry, 30 (1994), 30-33, cannot function as a photocatalyst, so hexachlorobenzene is dehalogenated in ethanol using cadmium sulfide as described in this document. It is impossible at all.
【００１３】本発明は、新規な光触媒及び還元力の優れ
た光触媒を提供し、このような光触媒を用いることによ
って、ハロゲン化物を最終的に燃焼処理になんら支障の
ない有機化合物まで導くのに十分な、光還元反応を誘導
することを目的とする。The present invention provides a novel photocatalyst and a photocatalyst having an excellent reducing power, and by using such a photocatalyst, it is possible to sufficiently convert a halide to an organic compound which finally does not hinder the combustion treatment. The purpose is to induce a photoreduction reaction.
【００１４】[0014]
【課題を解決するための手段】本発明は、ハロゲン化物
から脱ハロゲン化物を得るにあたり、前記ハロゲン化物
と、光触媒としての有機化合物半導体、硫化カドミウム
以外の金属硫化物又は１ｎｍ〜３０ｎｍの平均粒径を有
するナノサイズ微粒子の化合物半導体と、電子源とに光
を照射することによって、前記ハロゲン化物を脱ハロゲ
ン化し、前記ハロゲン化物を水素化する、脱ハロゲン化
物の製造方法に係るものである。According to the present invention, in obtaining a dehalogenated compound from a halide, the halide, an organic compound semiconductor as a photocatalyst, a metal sulfide other than cadmium sulfide, or an average particle size of 1 nm to 30 nm is used. The present invention relates to a method for producing a dehalogenated product, wherein the halide is dehalogenated and the halide is hydrogenated by irradiating a compound semiconductor of nano-sized fine particles having the following and an electron source with light.
【００１５】また、本発明は、ハロゲン化物から脱ハロ
ゲン化物を得るにあたり、前記ハロゲン化物と、光触媒
としての化合物半導体と、電子源としての有機アミンと
に光を照射することによって、前記ハロゲン化物を脱ハ
ロゲン化し、前記ハロゲン化物を水素化する、脱ハロゲ
ン化物の製造方法に係るものである。Further, in the present invention, in obtaining a dehalogenated compound from a halide, the halide, a compound semiconductor as a photocatalyst, and an organic amine as an electron source are irradiated with light to convert the halide. The present invention relates to a method for producing a dehalogenated product, comprising dehalogenating and hydrogenating the halide.
【００１６】本発明は、本発明者が、ハロゲン化物の脱
ハロゲン化において、ポリパラフェニレン等の新規な有
機化合物半導体や硫化亜鉛等の硫化カドミウム以外の金
属硫化物を光触媒として用いるのが極めて有効であるこ
とを見出したことに基づく。本発明者は、かかる光触媒
を用いれば、ポリハロゲン化合物を段階的に脱ハロゲン
化し、最終的に、燃焼処理においてなんら支障のない有
機化合物まで導くことができることを解明した。According to the present invention, it is extremely effective that the present inventor uses a novel organic compound semiconductor such as polyparaphenylene or a metal sulfide other than cadmium sulfide such as zinc sulfide as a photocatalyst in dehalogenation of a halide. Based on the finding that The present inventor has elucidated that the use of such a photocatalyst can dehalogenize a polyhalogen compound in a stepwise manner, and ultimately lead to an organic compound having no problem in the combustion treatment.
【００１７】また、本発明は、ハロゲン化物の脱ハロゲ
ン化において、１ｎｍ〜３０ｎｍ、特に、１ｎｍ〜１０
ｎｍの平均粒径を有するナノサイズ微粒子の化合物半導
体からなる光触媒が、極めて高い還元力を示すことに基
づく。Further, the present invention provides a method for dehalogenating a halide, which is 1 nm to 30 nm, particularly 1 nm to 10 nm.
This is based on the fact that a photocatalyst composed of a compound semiconductor of nano-sized fine particles having an average particle diameter of nm exhibits an extremely high reducing power.
【００１８】本発明者は、かかる光触媒を用いれば、ポ
リハロゲン化合物を段階的に脱ハロゲン化し、最終的に
は、燃焼処理になんら支障のない有機化合物にまで導く
ことが十分に可能であることを解明し、本発明を完成さ
せた。The present inventor has found that the use of such a photocatalyst makes it possible to dehalogenate a polyhalogen compound in a stepwise manner, and ultimately lead to an organic compound which does not hinder the combustion treatment. And completed the present invention.
【００１９】光触媒の平均粒径が１ｎｍ未満のものは、
合成するのが困難である。一方、光触媒の平均粒径が３
０ｎｍを超えるとき、還元反応に関わる伝導帯の電気化
学的位置が正側にシフトし、光触媒の還元力が低下する
ため、ハロゲン化物の還元ができなくなる問題がある。
光触媒の平均粒径は、１ｎｍ〜１０ｎｍがより一層好ま
しい。When the average particle diameter of the photocatalyst is less than 1 nm,
Difficult to synthesize. On the other hand, when the average particle size of the photocatalyst is 3
If it exceeds 0 nm, the electrochemical position of the conduction band involved in the reduction reaction shifts to the positive side, and the reducing power of the photocatalyst decreases, so that there is a problem that halide cannot be reduced.
The average particle size of the photocatalyst is more preferably 1 nm to 10 nm.
【００２０】さらに、本発明は、光触媒としての化合物
半導体を用いるハロゲン化物の脱ハロゲン化において、
トリエチルアミン等の有機アミンが著しく優れた電子源
として働くことに基づく。本発明者は、かかる有機アミ
ンを用いれば、極めて効率的にハロゲン化物の脱ハロゲ
ン化及び水素化を誘導することができることを突き止
め、本発明に到達した。Further, the present invention provides a method for dehalogenating a halide using a compound semiconductor as a photocatalyst,
It is based on the fact that organic amines such as triethylamine act as a remarkably excellent electron source. The present inventors have found that the use of such an organic amine can induce dehalogenation and hydrogenation of a halide extremely efficiently, and have reached the present invention.
【００２１】本発明の脱ハロゲン化物の製造方法は、光
触媒の還元力が高く、ハロゲン化物から効率的に脱ハロ
ゲン化物を得ることができるので、ポリハロゲン化合物
の解毒処理システムとして極めて有用である。The method for producing a dehalogenated product of the present invention is very useful as a system for detoxifying polyhalogen compounds, since the photocatalyst has a high reducing power and can efficiently obtain a dehalogenated product from the halide.
【００２２】また、本発明によれば、環境中の希薄な含
ハロゲン化合物の処理だけでなく、大量に存在する貯蔵
物中の有害ポリハロゲン化物、あるいは環境中から回収
された有害ポリハロゲン化物の処理を密閉系を用いて行
うことを可能とする。Further, according to the present invention, not only the treatment of a dilute halogen-containing compound in the environment but also the removal of a harmful polyhalide in a large amount of storage or a harmful polyhalide recovered from the environment. Processing can be performed using a closed system.
【００２３】[0023]
【発明の実施の形態】本発明で処理することができるハ
ロゲン化物は、特に限定されることなく、脱ハロゲン化
が可能である種々のあらゆる有機含ハロゲン化合物が含
まれる廃棄物であってもよい。有機含ハロゲン化合物と
しては、例えば、ダイオキシン、ポリクロロビフェニ
ル、ハロゲン化ベンゼン、ジハロゲン化ベンゼン、トリ
ハロゲン化ベンゼン、テトラハロゲン化ベンゼン、ペン
タハロゲン化ベンゼン、ヘキサハロゲン化ベンゼン、ハ
ロゲン化メタン、ジハロゲン化メタン、トリハロゲン化
メタン、テトラハロゲン化メタン、ハロゲン化エタン、
ジハロゲン化エタン、トリハロゲン化エタン、テトラハ
ロゲン化エタン、ペンタハロゲン化エタン、ヘキサハロ
ゲン化エタン、ハロゲン化エチレン、ジハロゲン化エチ
レン、トリハロゲン化エチレン、テトラハロゲン化エチ
レン等が挙げられる。DETAILED DESCRIPTION OF THE INVENTION The halide which can be treated in the present invention is not particularly limited, and may be a waste containing various organic halogen-containing compounds which can be dehalogenated. . Examples of organic halogen-containing compounds include, for example, dioxin, polychlorobiphenyl, halogenated benzene, dihalogenated benzene, trihalogenated benzene, tetrahalogenated benzene, pentahalogenated benzene, hexahalogenated benzene, halogenated methane, dihalogenated methane , Trihalogenated methane, tetrahalogenated methane, halogenated ethane,
Examples thereof include dihalogenated ethane, trihalogenated ethane, tetrahalogenated ethane, pentahalogenated ethane, hexahalogenated ethane, halogenated ethylene, dihalogenated ethylene, trihalogenated ethylene, and tetrahalogenated ethylene.
【００２４】本発明にかかる有機化合物半導体には、ポ
リパラフェニレン、ポリピリジン、ポリピリジン−２，
５−ジイル、ポリチオフェン、ポリピロール、ポリビニ
レンフェニレン、ポリビニレンピリジン、ポリビニレン
チオフェン、ポリビニレンチオフェン等が用いられる。The organic compound semiconductor according to the present invention includes polyparaphenylene, polypyridine, polypyridine-2,
5-diyl, polythiophene, polypyrrole, polyvinylenephenylene, polyvinylenepyridine, polyvinylenethiophene, polyvinylenethiophene, and the like are used.
【００２５】本発明にかかる硫化カドミウム以外の金属
硫化物には、硫化カドミウムを除き、硫化亜鉛、硫化
鉛、硫化ニッケル等を用いることができる。As the metal sulfide other than cadmium sulfide according to the present invention, zinc sulfide, lead sulfide, nickel sulfide and the like can be used except for cadmium sulfide.
【００２６】本発明にかかる化合物半導体には、有機化
合物半導体、及び硫化カドミウムを含む金属硫化物、酸
化チタン、酸化亜鉛、酸化ニオブ、酸化タンタル、酸化
ジルコニウム等の金属酸化物等の無機化合物半導体等を
用いることができる。The compound semiconductor according to the present invention includes organic compound semiconductors and inorganic compound semiconductors such as metal sulfides including cadmium sulfide, metal oxides such as titanium oxide, zinc oxide, niobium oxide, tantalum oxide and zirconium oxide. Can be used.
【００２７】本発明では、かかる化合物半導体を平均粒
径が１ｎｍ〜３０ｎｍ、特に、１ｎｍ〜１０ｎｍを有す
るナノサイズ微粒子として光触媒に用いることで、光触
媒に極めて高い還元力を発揮させることができる。In the present invention, by using such a compound semiconductor as nano-sized fine particles having an average particle diameter of 1 nm to 30 nm, particularly 1 nm to 10 nm, the photocatalyst can exhibit a very high reducing power.
【００２８】本発明にかかる電子源には、トリエチルア
ミン、ジエチルアミン、エチルアミン、トリメチルアミ
ン、ジメチルアミン、メチルアミン、トリエタノールア
ミン、ジエタノールアミン、エタノールアミン等の有機
アミン、又はメタノール、エタノール、ｎ−プロパノー
ル、２−プロパノール、ブタノール等のアルコールを用
いることができる。The electron source according to the present invention includes organic amines such as triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, triethanolamine, diethanolamine and ethanolamine, or methanol, ethanol, n-propanol, 2- Alcohols such as propanol and butanol can be used.
【００２９】特に、本発明では、電子源としてトリエチ
ルアミン等の有機アミンを用いる場合、光触媒としての
化合物半導体を、平均粒径のサイズに関わらず、用いる
ことができる。かかる有機アミンは、光還元反応におい
て、極めて優れた電子源として働き、極めて効率的にハ
ロゲン化物の脱ハロゲン化及び水素化を誘導することが
できる。In particular, in the present invention, when an organic amine such as triethylamine is used as the electron source, a compound semiconductor as a photocatalyst can be used regardless of the average particle size. Such an organic amine functions as an extremely excellent electron source in a photoreduction reaction, and can induce dehalogenation and hydrogenation of a halide very efficiently.
【００３０】本発明では、このようなポリハロゲン化物
と所定の光触媒と電子源とに光を照射することによっ
て、光触媒が光エネルギーを吸収して、励起電子を生成
し、この電子がハロゲン化物に注入されることを原理と
している。In the present invention, by irradiating such a polyhalide, a predetermined photocatalyst, and an electron source with light, the photocatalyst absorbs light energy to generate excited electrons, and the electrons are converted into halides. The principle is to be injected.
【００３１】本発明では、透明なパイレックス硝子製反
応器を用いることができ、この容器内で光触媒及び電子
源をＮ，Ｎ−ジメチルホルムアミド、テトラヒドロフラ
ン、アルコール類、水等の溶媒中に分散、あるいは溶解
し、ハロゲン化物を加えて、反応器内を窒素ガスで置換
する。In the present invention, a transparent Pyrex glass reactor can be used, in which a photocatalyst and an electron source are dispersed in a solvent such as N, N-dimethylformamide, tetrahydrofuran, alcohols, water, or the like. After dissolving and adding a halide, the inside of the reactor is replaced with nitrogen gas.
【００３２】本発明では、この反応器に光を照射する。
光には、紫外光が用いられるが、可視光を利用すること
ができる光触媒、例えば、硫化カドミウム、酸化鉄、ポ
リパラフェニレン、ポリピリジン等を用いる反応系で
は、可視光を用いることができる。In the present invention, the reactor is irradiated with light.
Ultraviolet light is used as light, but visible light can be used in a reaction system using a photocatalyst capable of utilizing visible light, such as cadmium sulfide, iron oxide, polyparaphenylene, or polypyridine.
【００３３】光照射されたポリハロゲン化物は、段階的
に脱ハロゲン化（ハロゲン分子がはずれて水素と置き換
わる）し、最終的には完全にハロゲン原子の除去が達成
できる。ハロゲン原子は、ハロゲン化水素として、系中
に残存する。このように、本発明においては、脱ハロゲ
ン反応だけが選択的に進行し、しかもポリハロゲン化化
合物に対して段階的に起こる（下記、実施例参照）。The light-irradiated polyhalide undergoes stepwise dehalogenation (halogen molecules are displaced by hydrogen), and ultimately complete removal of halogen atoms can be achieved. The halogen atom remains in the system as a hydrogen halide. As described above, in the present invention, only the dehalogenation reaction proceeds selectively, and occurs stepwise with respect to the polyhalogenated compound (see Examples below).
【００３４】従来の系、すなわち、酸化チタンを光触媒
として用い、酸化分解により、解毒する系では、種々の
中間体が生成する。例えば、４−クロロフェノールを酸
化チタン光触媒で酸化した場合に検出された生成物は７
種にもわたる。その内容は、ヒドロキシヒドロキノリ
ン、ヒドロキシベンゾキノン、フェノール、４−クロロ
カテコール、４−ヒドロキシフェニルベンゾキノン、
２，５，４′−とりヒドロキシビフェニル、５−クロロ
−２，４′ジヒドロキシビフェニルと報告されている
(J. Theurich et al., Langmuir 12,6368 (1996)参照)
。In a conventional system, that is, a system using titanium oxide as a photocatalyst and detoxifying by oxidative decomposition, various intermediates are produced. For example, when 4-chlorophenol is oxidized with a titanium oxide photocatalyst, the product detected is 7
Across seeds. Its contents include hydroxyhydroquinoline, hydroxybenzoquinone, phenol, 4-chlorocatechol, 4-hydroxyphenylbenzoquinone,
2,5,4'-Torhydroxybiphenyl and 5-chloro-2,4'dihydroxybiphenyl have been reported.
(See J. Theurich et al., Langmuir 12,6368 (1996))
.
【００３５】本発明は、常温で機能する光触媒を用い
て、還元的に含ハロゲン化合物を分解するものである。
この手法で必要なものは、光エネルギーであり、紫外線
光源又は太陽光を用いることができる。また、この還元
的プロセスでは、酸化プロセスにおいて生成する有害副
生成物が生成しないため、その利用価値が極めて高い。According to the present invention, a halogen-containing compound is reductively decomposed using a photocatalyst functioning at room temperature.
What is needed in this method is light energy, and an ultraviolet light source or sunlight can be used. In addition, in this reduction process, harmful by-products generated in the oxidation process are not generated, so that its utility value is extremely high.
【００３６】本発明の脱ハロゲン化物の製造方法によれ
ば、ダイオキシンを始めとする有害な含ハロゲン化合物
をより一層毒性の低い化合物に転換・分解することが可
能になり、地球規模で環境汚染問題をもたらす種々の化
学物質を解毒することができる。According to the method for producing a dehalogenated product of the present invention, it is possible to convert and decompose harmful halogen-containing compounds such as dioxins into compounds having even lower toxicity, and to reduce environmental pollution on a global scale. Can be detoxified.
【００３７】[0037]
【実施例】以下、本発明を実施例に基づいて説明する。実施例１ 硫化亜鉛ナノ微粒子による１，４−ジクロロベンゼンの
脱塩素化反応 硫化亜鉛ナノ微粒子（平均粒径２ｎｍ〜６ｎｍ）コロイ
ドを光触媒として用いて、１，４−ジクロロベンゼンの
脱塩素化反応を行った。５ｍＭの過塩素酸亜鉛を含む
Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）を試験管に入
れ、氷水中につけて冷却し、硫化水素ガスを吹き込むこ
とにより硫化亜鉛ナノ微粒子コロイド溶液を調製した。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Example 1 1,4-Dichlorobenzene by zinc sulfide nanoparticles
Dechlorination zinc sulfide nanoparticles with (average particle diameter 2 nm to 6 nm) colloidal as a photocatalyst, was dechlorination of 1,4-dichlorobenzene. N, N-dimethylformamide (DMF) containing 5 mM zinc perchlorate was placed in a test tube, cooled in ice water, and hydrogen sulfide gas was blown into the solution to prepare a zinc sulfide nanoparticle colloid solution.
【００３８】２．５ｍＭの硫化亜鉛、２５ｍＭの１，４
−ジクロロベンゼン、１Ｍのトリエチルアミンを含むＤ
ＭＦ溶液２ｍｌを調製し、内径８mmの円筒形バイレック
ス製反応管に入れ、窒素ガスで内部を完全に置換し、高
圧水銀灯により照射した。照射中反応管は冷却水によ
り、室温に保った。反応生成物はガスクロマトグラフに
より定量した。2.5 mM zinc sulfide, 25 mM 1,4
Dichlorobenzene, D containing 1 M triethylamine
2 ml of the MF solution was prepared, placed in a cylindrical Virex reaction tube having an inner diameter of 8 mm, the inside was completely replaced with nitrogen gas, and irradiated with a high-pressure mercury lamp. During the irradiation, the reaction tube was kept at room temperature with cooling water. The reaction products were quantified by gas chromatography.
【００３９】結果を図１に示す。図１では、ＺｎＳ存在
下の生成物の量を、１，４−ジクロロベンゼン（●）、
クロロベンゼン（▲）、ベンゼン（◆）、水素（■）で
示した。また、ＺｎＳ非存在下の生成物の量を、１，４
−ジクロロベンゼン（○）、クロロベンゼン（△）、ベ
ンゼン（◇）、水素（□）で示した。FIG. 1 shows the results. In FIG. 1, the amount of the product in the presence of ZnS is represented by 1,4-dichlorobenzene (●),
Chlorobenzene (▲), benzene (◆), hydrogen (■). Further, the amount of the product in the absence of ZnS was set to 1,4
-Dichlorobenzene (○), chlorobenzene (△), benzene (◇), hydrogen (□).
【００４０】図１に示すように、ＺｎＳ存在下で、光照
射とともにに１，４−ジクロロベンゼン（●）が減少
し、クロロベンゼン（▲）が生成し、さらに光照射時間
が長くなるにつれベンゼン（◆）の生成も見られた。こ
の生成物の挙動は、１，４−ジクロロベンゼンはまず、
脱塩素化を受けてクロロベンゼンとなり、さらにこのク
ロロベンゼンが脱塩素化を受ける逐次反応であることを
示している。この反応は、光触媒である硫化亜鉛ナノ微
粒子がなくとも進行するが、光触媒存在下では２〜５倍
に促進されることがわかった。ガスクロマトグラフで検
出された生成物は、クロロベンゼン、ベンゼンのみであ
った。As shown in FIG. 1, in the presence of ZnS, 1,4-dichlorobenzene (●) decreases with light irradiation, chlorobenzene (▲) is generated, and benzene ( ◆) was also observed. The behavior of this product is that 1,4-dichlorobenzene first
This shows that chlorobenzene is dechlorinated to be chlorobenzene, and this chlorobenzene is a sequential reaction to be dechlorinated. This reaction proceeds even without zinc sulfide nanoparticles as a photocatalyst, but was found to be accelerated 2 to 5 times in the presence of the photocatalyst. The products detected by gas chromatography were only chlorobenzene and benzene.
【００４１】実施例２ 硫化亜鉛ナノ微粒子による種々のクロロベンゼンの脱塩
素化反応 実施例１と同じ光触媒系を用いて、クロロベンゼン、
１，２−ジクロロベンゼン、１，３−ジクロロベンゼ
ン、１，４−ジクロロベンゼン、１，２，３−トリクロ
ロベンゼン、１，２，４−トリクロロベンゼン、１，
２，３，４−テトラクロロベンゼンの脱塩素化反応を行
った。光照射４〜５時間後の反応生成物組成を表１に示
す。 Example 2 Desalting of various chlorobenzenes with zinc sulfide nanoparticles
Using the same photocatalytic system and hydrogenation reaction in Example 1, chlorobenzene,
1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,
A dechlorination reaction of 2,3,4-tetrachlorobenzene was performed. Table 1 shows the composition of the reaction product 4 to 5 hours after light irradiation.
【００４２】[0042]
【表１】 [Table 1]
【００４３】表１に示されるように、これらの塩化ベン
ゼンの反応を行った場合にも、逐次的に脱塩素化反応が
進行していること、そして消失した反応物質と生成物と
の収支が合っていることから、反応は選択的な脱塩素化
だけが、逐次的に進行していることが判明した。１，
２，３，４−テトラクロロベンゼンの場合にも最終的に
はベンゼンにまで脱塩素化することも明らかとなった。As shown in Table 1, even when these benzene chlorides were reacted, it was found that the dechlorination reaction was proceeding sequentially, and that the balance between the disappeared reactants and the products was not exceeded. The agreement indicated that the reaction was proceeding only sequentially with selective dechlorination. 1,
In the case of 2,3,4-tetrachlorobenzene, it was also revealed that dechlorination was finally performed to benzene.
【００４４】実施例３ ポリパラフェニルによる１，２，３，４−テトラクロロ
ベンゼンの脱塩素化反応 ポリパラフェニレン（ＰＰＰ：重合度９〜１１）を光触
媒として用いて、１，２，３，４−テトラクロロベンゼ
ンの脱塩素化反応を行った。１ｍｇのＰＰＰ、２５ｍＭ
の１，２，３，４−テトラクロロベンゼン、１Ｍのトリ
エチルアミンを含むジメチルホルムアミド（ＤＭＦ）溶
液２ｍｌを調製し、内径８mmの円筒形パイレックス製反
応管に入れ、窒素ガスで内部を完全に置換し、高圧水銀
灯により照射した。照射中反応管は冷却水により、室温
に保った。反応生成物はガスクロマトグラフにより定量
した。 Example 3 1,2,3,4-Tetrachloro with polyparaphenyl
Dechlorination reaction of benzene Dechlorination reaction of 1,2,3,4-tetrachlorobenzene was performed using polyparaphenylene (PPP: degree of polymerization 9 to 11) as a photocatalyst. 1 mg of PPP, 25 mM
2 ml of a dimethylformamide (DMF) solution containing 1,2,3,4-tetrachlorobenzene and 1 M of triethylamine was prepared, put into a cylindrical Pyrex reaction tube having an inner diameter of 8 mm, and the inside was completely replaced with nitrogen gas. Irradiated with a high pressure mercury lamp. During the irradiation, the reaction tube was kept at room temperature with cooling water. The reaction products were quantified by gas chromatography.
【００４５】結果を図２に示す。図２では、生成物を、
それぞれ、１，２，３，４−テトラクロロベンゼン
（●）、１，２，４−トリクロロベンゼン（▽）、１，
２，３−トリクロロベンゼン（○）、１，２−ジクロロ
ベンゼン（△）、１，３−ジクロロベンゼン（□）、
１，４−ジクロロベンゼン（▲）及びクロロベンゼン
（◇）で示した。FIG. 2 shows the results. In FIG. 2, the product is
1,2,3,4-tetrachlorobenzene (●), 1,2,4-trichlorobenzene (▽), 1,
2,3-trichlorobenzene (○), 1,2-dichlorobenzene (△), 1,3-dichlorobenzene (□),
The results are shown in 1,4-dichlorobenzene (▲) and chlorobenzene (◇).
【００４６】図２に示すように、光照射とともに、１，
２，３，４−テトラクロロベンゼンが急激に減少し、
１，２，３−テトラクロロベンゼン、１，２，４−テト
ラクロロベンゼンが生成し、さらに光照射３時間後に
は、１，２−ジクロロベンゼン、１，３−ジクロロベン
ゼン、１，４−ジクロロベンゼンが生成し、クロロベン
ゼンの生成も見られた。この生成物の挙動は、１，２，
３，４−テトラクロロベンゼンはまず、脱塩素化を受け
てトリクロロベンゼンとなり、さらにこのトリクロロベ
ンゼンが脱塩素化を受けてジクロロベンゼン、クロロベ
ンゼンとなる逐次反応であることを示している。As shown in FIG. 2, together with the light irradiation,
2,3,4-tetrachlorobenzene sharply decreases,
1,2,3-tetrachlorobenzene and 1,2,4-tetrachlorobenzene are produced, and after 3 hours of light irradiation, 1,2-dichlorobenzene, 1,3-dichlorobenzene, and 1,4-dichlorobenzene are produced. The formation of chlorobenzene was also observed. The behavior of this product is 1, 2,
This shows that 3,4-tetrachlorobenzene is a sequential reaction in which trichlorobenzene is firstly dechlorinated into trichlorobenzene, and this trichlorobenzene is further dechlorinated into dichlorobenzene and chlorobenzene.
【００４７】実施例４ 可視光照射下におけるポリパラフェニレン（ＰＰＰ）に
よる１，２，３，４−テトラクロロベンゼンの脱塩素化
反応 実施例３とまったく同じ反応条件において、可視光を用
いた反応を行った。結果を図３に示す。図３では、ＰＰ
Ｐ存在下の生成物を、それぞれ、１，２，３，４−テト
ラクロロベンゼン（●）及び１，２，４−トリクロロベ
ンゼン（■）とし、ＰＰＰ非存在下の生成物を、それぞ
れ、１，２，３，４−テトラクロロベンゼン（○）及び
１，２，４−トリクロロベンゼン（□）とした。 Example 4 Polyparaphenylene (PPP) under visible light irradiation
Of 1,2,3,4-tetrachlorobenzene by chlorination
The reaction using visible light was performed under exactly the same reaction conditions as in Reaction Example 3. The results are shown in FIG. In FIG. 3, PP
The products in the presence of P were 1,2,3,4-tetrachlorobenzene (●) and 1,2,4-trichlorobenzene (■), respectively, and the products in the absence of PPP were 1,1, respectively. 2,3,4-tetrachlorobenzene (○) and 1,2,4-trichlorobenzene (□).
【００４８】図３に示すように、光照射とともに、１，
２，３，４−テトラクロロベンゼンが減少し、それにと
もない１，２，４−トリクロロベンゼンの生成が見られ
た。この反応は光触媒であるＰＰＰが無ければ進行しな
い。ＰＰＰを光触媒として用いれば、可視光照射下にお
ける脱塩素化反応が可能であることがわかった。As shown in FIG. 3, together with the light irradiation,
The amount of 2,3,4-tetrachlorobenzene was reduced, and accompanying this, the formation of 1,2,4-trichlorobenzene was observed. This reaction does not proceed without the photocatalyst PPP. It was found that the dechlorination reaction under visible light irradiation was possible if PPP was used as a photocatalyst.
【００４９】比較例１ 実施例１の実験を、硫化亜鉛ナノ微粒子の代わりに通常
のサイズの硫化亜鉛粉末（平均粒径１μｍ〜１０μｍ）
を用いて、他の条件は全く同じ条件で反応を行った。結
果は、光触媒を加えない場合の変化とほとんど一致し、
硫化亜鉛粉末（平均粒径１μｍ〜１０μｍ）が、ジクロ
ロベンゼンの還元反応に対する光触媒として機能しない
ことを示した。Comparative Example 1 The experiment of Example 1 was repeated, except that zinc sulfide nanoparticles were replaced with zinc sulfide powder of ordinary size (average particle size: 1 μm to 10 μm).
The reaction was carried out under exactly the same conditions as above. The results were almost consistent with the changes without the addition of photocatalyst,
It was shown that zinc sulfide powder (average particle size 1 μm to 10 μm) did not function as a photocatalyst for the reduction reaction of dichlorobenzene.
【００５０】本発明の脱ハロゲン化物の製造方法は、光
触媒の還元力が高く、ハロゲン化物から効率的に脱ハロ
ゲン化物を得ることができるので、ポリハロゲン化合物
の解毒処理システムとして極めて有用である。The process for producing a dehalogenated product of the present invention is extremely useful as a detoxification system for polyhalogen compounds, since the photocatalyst has a high reducing power and can efficiently obtain a dehalogenated product from the halide.
【００５１】また、本発明によれば、環境中の希薄な含
ハロゲン化合物の処理だけでなく、大量に存在する貯蔵
物中の有害ポリハロゲン化物、あるいは環境中から回収
された有害ポリハロゲン化物の処理を密閉系を用いて極
めて効率よく行うことができる。Further, according to the present invention, not only the treatment of a dilute halogen-containing compound in the environment but also the removal of a harmful polyhalide in a large amount of storage or a harmful polyhalide recovered from the environment. Processing can be performed very efficiently using a closed system.
【図１】経時的な反応生成物の量を示すグラフである。FIG. 1 is a graph showing the amount of reaction product over time.
【図２】経時的な反応生成物の量を示すグラフである。FIG. 2 is a graph showing the amount of a reaction product over time.
【図３】経時的な反応生成物の量を示すグラフである。FIG. 3 is a graph showing the amount of a reaction product over time.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年２月７日（２０００．２．７）[Submission date] February 7, 2000 (2000.2.7)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Correction target item name] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Correction target item name] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Correction target item name] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項５[Correction target item name] Claim 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１３】本発明は、ハロゲン化物の脱ハロゲン化に
おいて新規な光触媒及び還元力の優れた光触媒を提供
し、このような光触媒を用いることによって、ハロゲン
化物を最終的に燃焼処理になんら支障のない有機化合物
まで導くのに十分な、光還元反応を誘導することを目的
とする。[0013] The present invention relates to the dehalogenation of halides.
A new photocatalyst and a photocatalyst with excellent reducing power, and by using such a photocatalyst, a photoreduction reaction sufficient to eventually lead the halide to an organic compound that does not hinder the combustion treatment at all. The purpose is to induce.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１４】[0014]
【課題を解決するための手段】本発明は、ハロゲン化物
から脱ハロゲン化物を得るにあたり、Ｎ，Ｎ−ジメチル
ホルムアミド、テトラヒドロフラン及びアルコール類か
らなる群より選ばれた少なくとも１種の溶媒中で、前記
ハロゲン化物と、光触媒としての有機化合物半導体、硫
化カドミウム以外の金属硫化物又は１ｎｍ〜３０ｎｍの
平均粒径を有するナノサイズ微粒子の化合物半導体と、
電子源とに光を照射することによって、前記ハロゲン化
物を脱ハロゲン化し、前記ハロゲン化物を水素化する、
脱ハロゲン化物の製造方法に係るものである。SUMMARY OF THE INVENTION The present invention relates to a method for obtaining a dehalogenated compound from a halide, by using N, N-dimethyl
Formamide, tetrahydrofuran and alcohols
In at least one solvent selected from the group consisting of the above, the halide, an organic compound semiconductor as a photocatalyst, a metal sulfide other than cadmium sulfide, or a compound semiconductor of nano-sized fine particles having an average particle diameter of 1 nm to 30 nm When,
By irradiating the electron source with light, the halide is dehalogenated, and the halide is hydrogenated.
The present invention relates to a method for producing a dehalogenated product.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Correction target item name] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１５】また、本発明は、ハロゲン化物から脱ハロ
ゲン化物を得るにあたり、Ｎ，Ｎ−ジメチルホルムアミ
ド、テトラヒドロフラン及びアルコール類からなる群よ
り選ばれた少なくとも１種の溶媒中で、前記ハロゲン化
物と、光触媒としての化合物半導体と、電子源としての
有機アミンとに光を照射することによって、前記ハロゲ
ン化物を脱ハロゲン化し、前記ハロゲン化物を水素化す
る、脱ハロゲン化物の製造方法に係るものである。Further, the present invention relates to a method for obtaining a dehalogenated compound from a halide, wherein N, N-dimethylformamide is used.
From the group consisting of alcohols, tetrahydrofuran and alcohols
Irradiating the halide, a compound semiconductor as a photocatalyst, and an organic amine as an electron source with light in at least one selected solvent to dehalogenate the halide; And a method for producing a dehalogenated product.
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３１[Correction target item name] 0031
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３１】本発明では、透明なパイレックス硝子製反
応器を用いることができ、この容器内で光触媒及び電子
源をＮ，Ｎ−ジメチルホルムアミド、テトラヒドロフラ
ン、アルコール類等の溶媒中に分散、あるいは溶解し、
ハロゲン化物を加えて、反応器内を窒素ガスで置換す
る。In the present invention, a transparent Pyrex glass reactor can be used. In this vessel, the photocatalyst and the electron source are dispersed or dissolved in a solvent such as N, N-dimethylformamide, tetrahydrofuran, alcohols or the like. ,
A halide is added, and the inside of the reactor is replaced with nitrogen gas.
【手続補正９】[Procedure amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００３４[Correction target item name] 0034
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００３４】従来の系、すなわち、酸化チタンを光触媒
として用い、酸化分解により、解毒する系では、種々の
中間体が生成する。例えば、４−クロロフェノールを酸
化チタン光触媒で酸化した場合に検出された生成物は７
種にもわたる。その内容は、ヒドロキシヒドロキノリ
ン、ヒドロキシベンゾキノン、フェノール、４−クロロ
カテコール、４−ヒドロキシフェニルベンゾキノン、
２，５，４′−トリヒドロキシビフェニル、５−クロロ
−２，４′ジヒドロキシビフェニルと報告されている
(J. Theurich et al., Langmuir 12,6368 (1996)参照)
。In a conventional system, that is, a system using titanium oxide as a photocatalyst and detoxifying by oxidative decomposition, various intermediates are produced. For example, when 4-chlorophenol is oxidized with a titanium oxide photocatalyst, the product detected is 7
Across seeds. Its contents include hydroxyhydroquinoline, hydroxybenzoquinone, phenol, 4-chlorocatechol, 4-hydroxyphenylbenzoquinone,
Reported as 2,5,4' - trihydroxybiphenyl and 5-chloro-2,4'dihydroxybiphenyl
(See J. Theurich et al., Langmuir 12,6368 (1996))
.
【手続補正１０】[Procedure amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４８[Correction target item name] 0048
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４８】図３に示すように、光照射とともに、１，
２，３，４−テトラクロロベンゼンが減少し、それにと
もない１，２，４−トリクロロベンゼンの生成が見られ
た。As shown in FIG. 3, together with the light irradiation,
The amount of 2,3,4-tetrachlorobenzene was reduced, and accompanying this, the formation of 1,2,4-trichlorobenzene was observed.
【手続補正１１】[Procedure amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４９[Correction target item name] 0049
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４９】この反応は光触媒であるＰＰＰが無ければ
進行しない。ＰＰＰを光触媒として用いれば、可視光照
射下における脱塩素化反応が可能であることがわかっ
た。This reaction does not proceed without PPP as a photocatalyst. It was found that the dechlorination reaction under visible light irradiation was possible if PPP was used as a photocatalyst.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 35/02 Ｂ０１Ｊ 35/02 Ｊ Ｈ Ｃ０７Ｂ 61/00 Ｃ０７Ｂ 61/00 Ｄ ３００ ３００ Ｆターム(参考） 2E191 BA12 BC01 BD13 BD17 4G069 AA02 BA22A BA22B BA48A BB09A BB09B BC35B BE02A BE02B BE14A BE21A BE37A BE37B BE38A CB02 CB66 DA05 EB18Y EB19 ED10 4G075 AA13 BA05 CA33 4H006 AA02 AC13 BA95 BJ50 FC50 4H039 CA20 CG20 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 35/02 B01J 35/02 JH C07B 61/00 C07B 61/00 D 300 300 F-term (reference) 2E191 BA12 BC01 BD13 BD17 4G069 AA02 BA22A BA22B BA48A BB09A BB09B BC35B BE02A BE02B BE14A BE21A BE37A BE37B BE38A CB02 CB66 DA05 EB18Y EB19 ED10 4G075 AA13 BA05 CA33 4H006 AA20 AC13 BA95BJ39
Claims (6)
にあたり、 前記ハロゲン化物と、光触媒としての有機化合物半導体
と、電子源とに光を照射することによって、前記ハロゲ
ン化物を脱ハロゲン化し、前記ハロゲン化物を水素化す
ることを特徴とする、脱ハロゲン化物の製造方法。In obtaining a dehalide from a halide, the halide, an organic compound semiconductor as a photocatalyst, and an electron source are irradiated with light to dehalogenate the halide, thereby obtaining the halide. And a method for producing a dehalogenated product.
ニレン、ポリピリジン、ポリチオフェン、ポリピロー
ル、ポリビニレンフェニレン、ポリビニレンピリジン、
ポリビニレンチオフェン及びポリビニレンチオフェンか
らなる群より選ばれた少なくとも１種の化合物であるこ
とを特徴とする、請求項１記載の脱ハロゲン化物の製造
方法。2. The method according to claim 1, wherein the organic compound semiconductor is polyparaphenylene, polypyridine, polythiophene, polypyrrole, polyvinylenephenylene, polyvinylenepyridine,
The method for producing a dehalogenated product according to claim 1, wherein the method is at least one compound selected from the group consisting of polyvinylenethiophene and polyvinylenethiophene.
にあたり、 前記ハロゲン化物と、硫化カドミウム以外の光触媒とし
ての金属硫化物と、電子源とに光を照射することによっ
て、前記ハロゲン化物を脱ハロゲン化し、前記ハロゲン
化物を水素化することを特徴とする、脱ハロゲン化物の
製造方法。3. In obtaining a dehalide from a halide, the halide is dehalogenated by irradiating the halide, a metal sulfide other than cadmium sulfide as a photocatalyst, and an electron source with light. And a method for producing a dehalogenated product, comprising hydrogenating the halide.
にあたり、 前記ハロゲン化物と、光触媒としての１ｎｍ〜３０ｎｍ
の平均粒径を有するナノサイズ微粒子の化合物半導体
と、電子源とに光を照射することによって、前記ハロゲ
ン化物を脱ハロゲン化し、前記ハロゲン化物を水素化す
ることを特徴とする、脱ハロゲン化物の製造方法。4. A method for obtaining a dehalogenated product from a halide, wherein the halide is combined with 1 nm to 30 nm as a photocatalyst.
By irradiating the compound semiconductor of nano-sized fine particles having an average particle size and light to an electron source, the halide is dehalogenated, and the halide is hydrogenated. Production method.
にあたり、 前記ハロゲン化物と、光触媒としての化合物半導体と、
電子源としての有機アミンとに光を照射することによっ
て、前記ハロゲン化物を脱ハロゲン化し、前記ハロゲン
化物を水素化することを特徴とする、脱ハロゲン化物の
製造方法。5. A method for obtaining a dehalogenated compound from a halide, wherein the halide, a compound semiconductor as a photocatalyst,
A method for producing a dehalogenated product, comprising irradiating an organic amine as an electron source with light to dehalogenate the halide and hydrogenate the halide.
とする、請求項１〜５のいずれか１項記載の脱ハロゲン
化物の製造方法。6. The method for producing a dehalogenated product according to claim 1, wherein visible light is used as the light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10309968A JP2000136151A (en) | 1998-10-30 | 1998-10-30 | Production of dehalogenated compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10309968A JP2000136151A (en) | 1998-10-30 | 1998-10-30 | Production of dehalogenated compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000136151A true JP2000136151A (en) | 2000-05-16 |
Family
ID=17999543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10309968A Pending JP2000136151A (en) | 1998-10-30 | 1998-10-30 | Production of dehalogenated compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000136151A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030084177A (en) * | 2002-04-25 | 2003-11-01 | 한국화학연구원 | Nano-fabricated TiO2 photocatalyst placed in zeolite framework and its manufacturing method and thereby removal method of ammonia-nitrogen |
| JP2021037465A (en) * | 2019-09-03 | 2021-03-11 | 国立大学法人東京工業大学 | Aromatic ring redox photocatalyst having high reduction power |
-
1998
- 1998-10-30 JP JP10309968A patent/JP2000136151A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030084177A (en) * | 2002-04-25 | 2003-11-01 | 한국화학연구원 | Nano-fabricated TiO2 photocatalyst placed in zeolite framework and its manufacturing method and thereby removal method of ammonia-nitrogen |
| JP2021037465A (en) * | 2019-09-03 | 2021-03-11 | 国立大学法人東京工業大学 | Aromatic ring redox photocatalyst having high reduction power |
| JP7341464B2 (en) | 2019-09-03 | 2023-09-11 | 学校法人日本工業大学 | Aromatic ring photoredox catalyst with high reducing power |
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