JPH01224202A - Method for recovering iodine from organic iodine compound-containing waste liquor - Google Patents
Method for recovering iodine from organic iodine compound-containing waste liquorInfo
- Publication number
- JPH01224202A JPH01224202A JP63048733A JP4873388A JPH01224202A JP H01224202 A JPH01224202 A JP H01224202A JP 63048733 A JP63048733 A JP 63048733A JP 4873388 A JP4873388 A JP 4873388A JP H01224202 A JPH01224202 A JP H01224202A
- Authority
- JP
- Japan
- Prior art keywords
- iodine
- waste liquor
- organic
- compound
- acid
- 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.)
- Granted
Links
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 47
- 239000011630 iodine Substances 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000005527 organic iodine compounds Chemical class 0.000 title claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 239000002872 contrast media Substances 0.000 abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- GVZPOILYKLKCDM-UHFFFAOYSA-N 5-amino-2-iodobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=C(I)C(C(O)=O)=C1 GVZPOILYKLKCDM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 238000006192 iodination reaction Methods 0.000 abstract description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 2
- 229940039231 contrast media Drugs 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 230000002070 germicidal effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005831 deiodination reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 1
- JEZJSNULLBSYHV-UHFFFAOYSA-N 5-amino-2,4,6-triiodobenzene-1,3-dicarboxylic acid Chemical compound NC1=C(I)C(C(O)=O)=C(I)C(C(O)=O)=C1I JEZJSNULLBSYHV-UHFFFAOYSA-N 0.000 description 1
- ICBAWCYWFNIQKQ-UHFFFAOYSA-N 5-amino-4-iodobenzene-1,3-dicarboxylic acid Chemical compound C1=C(C=C(C(=C1C(=O)O)I)N)C(=O)O ICBAWCYWFNIQKQ-UHFFFAOYSA-N 0.000 description 1
- KBZFDRWPMZESDI-UHFFFAOYSA-N 5-aminobenzene-1,3-dicarboxylic acid Chemical compound NC1=CC(C(O)=O)=CC(C(O)=O)=C1 KBZFDRWPMZESDI-UHFFFAOYSA-N 0.000 description 1
- GNOGSFBXBWBTIG-UHFFFAOYSA-N Acetrizoic acid Chemical compound CC(=O)NC1=C(I)C=C(I)C(C(O)=O)=C1I GNOGSFBXBWBTIG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- YVPYQUNUQOZFHG-UHFFFAOYSA-N amidotrizoic acid Chemical compound CC(=O)NC1=C(I)C(NC(C)=O)=C(I)C(C(O)=O)=C1I YVPYQUNUQOZFHG-UHFFFAOYSA-N 0.000 description 1
- -1 aromatic organic iodine compound Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000000750 industrial fungicide Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- XQZXYNRDCRIARQ-LURJTMIESA-N iopamidol Chemical compound C[C@H](O)C(=O)NC1=C(I)C(C(=O)NC(CO)CO)=C(I)C(C(=O)NC(CO)CO)=C1I XQZXYNRDCRIARQ-LURJTMIESA-N 0.000 description 1
- 229960004647 iopamidol Drugs 0.000 description 1
- NRXQIUSYPAHGNM-UHFFFAOYSA-N ioxynil Chemical compound OC1=C(I)C=C(C#N)C=C1I NRXQIUSYPAHGNM-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WCYAALZQFZMMOM-UHFFFAOYSA-N methanol;sulfuric acid Chemical compound OC.OS(O)(=O)=O WCYAALZQFZMMOM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、有機沃素化合物を含有する廃液から沃素を回
収する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for recovering iodine from waste liquid containing organic iodine compounds.
沃素は、工業的にレントゲン造影剤、工業用殺菌剤、農
園芸用除草剤等の原料として広く用いられているほか、
有機化合物の脱水素、異性化、縮合反応の触媒としてし
ばしば用いられており、工業的に極めて貴重な資源であ
る。Iodine is widely used industrially as a raw material for X-ray contrast agents, industrial fungicides, agricultural and horticultural herbicides, etc.
It is often used as a catalyst for dehydrogenation, isomerization, and condensation reactions of organic compounds, and is an extremely valuable resource industrially.
［従来の技術］
従来より、沃素の回収に関しては、種々の提案がなされ
ており、例えば、特公昭４６−５８１４号及び特公昭４
６−３５２４４号には、沃化アルキルとして存在する放
射性沃素を除去するための吸着剤に関する記載があり、
特公昭４８−４２３５７号には、触媒として沃素を使用
する有機物の気相脱水素反応において、反応系から排出
する反応混合気体を高温下で酸化銅と接触させ、次いで
一部沃素化された酸化銅を酸化側で酸化し、沃素を遊離
させ回収する方法についての記載がある。また、特開昭
５１−３４８９６号には、沃素又は沃素化合物を含有す
る廃棄物を燃焼炉にて燃焼させ、この燃焼ガス中の沃素
をアルカリ性のチオ硫酸ナトリウム又は亜硫酸ナトリウ
ムの水溶液に吸収させ、沃素を回収する記載がある。[Prior Art] Conventionally, various proposals have been made regarding the recovery of iodine.
No. 6-35244 describes an adsorbent for removing radioactive iodine present as alkyl iodide,
Japanese Patent Publication No. 48-42357 discloses that in a gas-phase dehydrogenation reaction of an organic substance using iodine as a catalyst, the reaction mixture discharged from the reaction system is brought into contact with copper oxide at high temperature, and then partially iodized oxide is brought into contact with copper oxide. There is a description of a method of oxidizing copper on the oxidation side to liberate and recover iodine. Furthermore, JP-A-51-34896 discloses that waste containing iodine or iodine compounds is burned in a combustion furnace, and the iodine in the combustion gas is absorbed into an alkaline sodium thiosulfate or sodium sulfite aqueous solution. There is a description of recovering iodine.
また、芳香族有機沃素化合物からの沃素の回収方法とし
ては、ＥＰ １０６９３４号に銅系触媒の存在下、強ア
ルカリと加熱処理することにより沃素を回収する記載が
ある。Further, as a method for recovering iodine from an aromatic organic iodine compound, EP 106934 describes recovering iodine by heat treatment with a strong alkali in the presence of a copper-based catalyst.
［発明が解決しようとする課題］
近年、有機沃素化合物、特にレントゲン造影剤及び工業
用殺菌剤の伸びは著しく、沃素は逼迫した状態となって
いる。一方、これら有機沃素化合物は極めて復雑な構造
を有するため、多数の工程を経て製造されている。[Problems to be Solved by the Invention] In recent years, the demand for organic iodine compounds, particularly X-ray contrast agents and industrial disinfectants, has increased significantly, and iodine has become scarce. On the other hand, since these organic iodine compounds have extremely complex structures, they are manufactured through a large number of steps.
当然、各工程毎に廃液が発生し、高価な沃素が副生物、
中間体等の種々の有機沃素化合物として廃液中に失われ
る。このような沃素の損失は、目的のレントゲン造影剤
もしくは殺菌剤の構造が複雑なほど多く、化合物によっ
ては、原料として用いる沃素の５０〜７０％が失われる
ものもある。Naturally, waste fluid is generated in each process, and expensive iodine is a by-product.
Lost in wastewater as various organic iodine compounds such as intermediates. Such loss of iodine increases as the structure of the target X-ray contrast agent or bactericidal agent becomes more complex, and depending on the compound, 50 to 70% of the iodine used as a raw material may be lost.
本発明は有機沃素化合物の製造において、発生した廃液
から、工業的に沃素を回収し、再利用する方法を提供す
ることを課題とする。An object of the present invention is to provide a method for industrially recovering and reusing iodine from waste liquid generated in the production of organic iodine compounds.
［課題を解決するための手段及び作用］本発明者らは、
上記した課題を達成するために鋭意検討した結果、有機
沃素化合物を含有する廃液を電解還元したのち、電解処
理液を酸化剤で酸化することにより本発明の課題が達成
されることを見出し、本発明を完成させるに至った。[Means and effects for solving the problem] The present inventors
As a result of intensive studies to achieve the above-mentioned objects, it was discovered that the objects of the present invention can be achieved by electrolytically reducing the waste liquid containing organic iodine compounds and then oxidizing the electrolytically treated liquid with an oxidizing agent. The invention was completed.
すなわち本発明は、
有機沃素化合物を含有する廃液を電解還元したのち、酸
化し沃素を遊離せしめることを特徴とする沃素の回収方
法である。That is, the present invention is an iodine recovery method characterized in that a waste solution containing an organic iodine compound is electrolytically reduced and then oxidized to liberate iodine.
一般に、有機沃素化合物が電解還元により脱沃素化反応
を起こすことはよく知られている。It is generally well known that organic iodine compounds undergo a deiodination reaction by electrolytic reduction.
しかし、本発明のように廃液中の有機沃素化合物を電解
還元により脱灰素化することによる、沃素の回収に応用
する技術は知られていない。However, as in the present invention, no technology is known that is applied to the recovery of iodine by deashing organic iodine compounds in waste liquid by electrolytic reduction.
本発明で用いる廃液は、ジアドリゾ酸（３，５−ジアセ
チルアミノ−２，４，６−トリヨード安息香酸）、アセ
トリゾ酸（３−アセチルアミノ−２，４，６−トリヨー
ド安息香酸）、イオパミドール等のレントゲン造影剤、
３，５−ジアミノ−２，４，６−トリヨード安息香酸、
５−アミノ−２，４，６−）リョードイソフタル酸等の
レントゲン造影剤の中間体または農園芸用除草剤アイオ
キシニル、工業用殺閉剤トリルショートメチルスルホン
等の製造に際し、発生する反応廃液、洗浄液、再結晶廃
液、酸析廃液等、又はこれらの混合物であるが、必ずし
もこれらに限定されるものではない、これらの廃液は適
宜ＰＨ４ｌｌ整を行った後使用される。The waste liquid used in the present invention includes diadorizoic acid (3,5-diacetylamino-2,4,6-triiodobenzoic acid), acetolizoic acid (3-acetylamino-2,4,6-triiodobenzoic acid), iopamidol, etc. X-ray contrast agent,
3,5-diamino-2,4,6-triiodobenzoic acid,
Reaction waste liquid generated during the production of intermediates for X-ray contrast agents such as 5-amino-2,4,6-) rhodoisophthalic acid, the agricultural and horticultural herbicide ioxynil, and the industrial occlusive agent tolyl short methyl sulfone, These waste liquids include, but are not limited to, cleaning liquids, recrystallization waste liquids, acid precipitation waste liquids, etc., and are not necessarily limited to these.These waste liquids are used after appropriately adjusting the pH to 411.
本発明の電解還元は、通常中央に隔膜を設けた陽極室及
び陰極室よりなる電解槽中にて行われる。The electrolytic reduction of the present invention is usually carried out in an electrolytic cell consisting of an anode chamber and a cathode chamber provided with a diaphragm in the center.
隔膜としては、カチオン交換膜の他アスベスト、セラミ
ックス等も使用可能であるが、カチオン交換膜が好適で
ある。As the diaphragm, in addition to the cation exchange membrane, asbestos, ceramics, etc. can also be used, but the cation exchange membrane is preferred.
また、陽極室は通常硫酸溶液及び陽極より構成されてお
り、陰極室は目的とする処理液及び陰極より構成されて
いる。Further, the anode chamber usually consists of a sulfuric acid solution and an anode, and the cathode chamber consists of a target treatment solution and a cathode.
また、陰極室には必要なら、支持電解質として相当量の
塩類、酸または塩基を溶解させ、廃液のｉｔ性を上げて
やるのがよいが、一般には廃液それ自体に既に十分な量
の塩類が含まれている場合が多く、支持電解質の添加は
不要な場合が多い。In addition, if necessary, it is advisable to dissolve a considerable amount of salts, acids, or bases as supporting electrolytes in the cathode chamber to increase the IT properties of the waste solution, but generally the waste solution itself already contains a sufficient amount of salts. In many cases, the addition of a supporting electrolyte is unnecessary.
陽極室における硫酸溶液の濃度としては、特に制限され
ず広い範囲内から適宜選択できるが、通常１〜２０重量
％硫酸水溶液又は硫酸アルコール溶液、好ましくは５〜
１０重量％硫酸水溶液又は硫酸アルコール溶液を使用す
るのがよい。The concentration of the sulfuric acid solution in the anode chamber is not particularly limited and can be appropriately selected from a wide range, but it is usually 1 to 20% by weight aqueous sulfuric acid solution or alcoholic sulfuric acid solution, preferably 5 to 20% by weight.
It is preferable to use a 10% by weight aqueous sulfuric acid solution or a sulfuric alcohol solution.
陽極としては、硫酸溶液により溶解されないものである
かぎり、いずれも公知のものを使用でき、例えば鉛、鉛
合金、白金、金、銀、ニッケル、ニンケル合金、亜鉛、
亜鉛合金、カドミウム、黒鉛、炭素等を挙げることがで
きる。これらの内でも、鉛や白金を使用するのが好まし
い、陰極としては鉛、亜鉛、ニッケル、白金、黒鉛、炭
素、酸化鉛、酸化ニッケル、酸化マンガン、酸化鉄、金
、ルテニウムまたはイリジウム、ルビジウム等の貴金属
で被覆された金属等を挙げることができるが、鉛、亜鉛
、ニッケル等が好適である。As the anode, any known material can be used as long as it is not dissolved by the sulfuric acid solution, such as lead, lead alloy, platinum, gold, silver, nickel, nickel alloy, zinc,
Zinc alloys, cadmium, graphite, carbon, etc. can be mentioned. Among these, it is preferable to use lead or platinum.As the cathode, lead, zinc, nickel, platinum, graphite, carbon, lead oxide, nickel oxide, manganese oxide, iron oxide, gold, ruthenium or iridium, rubidium, etc. Examples include metals coated with noble metals, among which lead, zinc, nickel, etc. are preferable.
本発明の電解還元において、還元方法としては定電圧法
及び定電流法のいずれでも可能であるが、定電流法によ
るのが好ましい。In the electrolytic reduction of the present invention, either a constant voltage method or a constant current method can be used as the reduction method, but a constant current method is preferable.
定電流法を採用する場合、電流密度は通常０．１〜ＩＯ
Ａ／ｄａ”、好ましくは０．５〜３Ａ／ｄａ”である。When using the constant current method, the current density is usually 0.1 to IO
A/da", preferably 0.5 to 3 A/da".
電解反応に必要な通電量としては、電解槽の形状、電極
の種類、基質反応性等により一定しないが、通常５〜６
Ｆ１モル程度の電気量を通電すればよい。The amount of current required for the electrolytic reaction varies depending on the shape of the electrolytic cell, type of electrode, substrate reactivity, etc., but is usually 5 to 6 volts.
An amount of electricity of approximately 1 mole of F may be applied.
有機沃素化合物の電解還元による脱沃素化反応の電位は
、他の大多数の官能基の還元電位よりも低く、そのため
、種々の有機化合物の混合物であっても、最も早く還元
反応を受けるのは脱沃素化反応であり、その結果高い電
流効率が得られる結果となる。The potential of the deiodination reaction by electrolytic reduction of organic iodine compounds is lower than the reduction potential of most other functional groups. Therefore, even in a mixture of various organic compounds, the one that undergoes the reduction reaction fastest is This is a deiodination reaction, resulting in high current efficiency.
該電解温度は、通常０〜８０°Ｃ３好ましくは３０〜６
０°Ｃの範囲で行う、電解温度が低すぎると反応が進行
せず、逆に高すぎると大量の廃液を高温にする必要があ
り経済的見地から好ましくない。The electrolysis temperature is usually 0 to 80°C, preferably 30 to 6°C.
If the electrolysis temperature, which is carried out in the range of 0°C, is too low, the reaction will not proceed, and if it is too high, it will be necessary to heat a large amount of waste liquid to a high temperature, which is not preferred from an economical point of view.
反応時間は、電解還元の温度、電極材料、電解電流、廃
液中の有機沃素化合物の濃度により変わるが、通常攪拌
下１〜１５時間反応させればよい。The reaction time varies depending on the temperature of electrolytic reduction, the electrode material, the electrolytic current, and the concentration of the organic iodine compound in the waste liquid, but it is usually sufficient to carry out the reaction for 1 to 15 hours with stirring.
この電解還元は、回分式でも連続式でも行うことが可能
である。This electrolytic reduction can be performed either batchwise or continuously.
電解還元による脱灰素化反応終了後、処理液を酸化剤で
酸化すると沃素が遊離する。After the demineralization reaction by electrolytic reduction is completed, the treated solution is oxidized with an oxidizing agent to liberate iodine.
酸化剤としては、過酸化水素、次亜塩素酸ナトリウム、
塩素、亜硝酸ナトリウム等が挙げられる。Oxidizing agents include hydrogen peroxide, sodium hypochlorite,
Examples include chlorine and sodium nitrite.
かくして得られた遊離の沃素は、空気を導入することに
より処理液から追い出し、水酸化ナトリウム、水酸化カ
リウム等のアルカリ水溶液または、アルカリ性のチオ硫
酸ナトリウム、亜硫酸ナトリウム等の還元性水溶液に吸
収させる（ブローイングアウト法）、又は、遊離した沃
素を活性炭に吸着固定させる（活性炭法）、又は、イオ
ン交換樹脂に吸着固定させる（イオン交換樹脂法）等の
周知の方法により回収し、沃素として再利用することが
可能である。The free iodine thus obtained is expelled from the treatment solution by introducing air and absorbed into an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, or an alkaline reducing aqueous solution such as sodium thiosulfate or sodium sulfite ( The free iodine is recovered by well-known methods such as blowing out method), adsorption and fixation on activated carbon (activated carbon method), or adsorption and fixation on ion exchange resin (ion exchange resin method), and reused as iodine. Is possible.
沃素は極めて腐食性の大きい元素であり、従って、−Ｃ
に沃素回収装置の構成材料の選択及び設計は極めて困難
である。Iodine is an extremely corrosive element, and therefore -C
The selection and design of constituent materials for iodine recovery equipment is extremely difficult.
ところが、本発明では低温かつ還元性の条件下での回収
であり、沃素の腐食作用は極度に抑えられる。従来技術
のように高温または酸化性の条件下で遊離沃素又は沃化
塩を処理しないため、構成材料の選定及び設計が、他の
公知の沃素回収装置よりも格段に容易になる大きな利点
を有している。However, in the present invention, recovery is performed under low temperature and reducing conditions, and the corrosive effect of iodine is extremely suppressed. Since free iodine or iodide salts are not processed under high temperature or oxidizing conditions as in the prior art, the selection and design of constituent materials is significantly easier than with other known iodine recovery devices, which is a major advantage. are doing.
次に、実施例により本発明の方法を具体的に説明する。 Next, the method of the present invention will be specifically explained using examples.
実施例１
試料廃液として５−アミノ−２，４，６−トリヨードイ
ソフタル酸製造において生じた廃液を用いた。Example 1 A waste liquid produced in the production of 5-amino-2,4,6-triiodoisophthalic acid was used as a sample waste liquid.
試料廃液の調整は次の通りであった。The sample waste liquid was prepared as follows.
水４８００ｄと５−アミノイソフタル酸１８２ｇを反応
器に仕込み、ＰＲ拌しなから９０°Ｃに昇温した。4,800 d of water and 182 g of 5-aminoisophthalic acid were charged into a reactor, and the temperature was raised to 90°C without stirring.
次に、−塩化沃素５３６ｇを約１時間で滴下した。Next, 536 g of iodine chloride was added dropwise over about 1 hour.
その後、約５時間同温度で攪拌したのち室温まで冷却し
た。結晶を濾別し、１０００ｄの水で洗浄した。Thereafter, the mixture was stirred at the same temperature for about 5 hours and then cooled to room temperature. The crystals were filtered off and washed with 1000 d of water.
反応濾液及び洗浄液を合わせ５５００ｄの試料用廃液を
得た。この廃液中には、５−アミノ−２−ヨードイソフ
タル酸、Ｓ−アミノ−４−ヨードイソフタル酸、５−ア
ミノ−２，４−ショートイソフタル酸、５−アミノ−４
，６−ショートイソフタル酸、５−アミノ−２，４，６
−ドリヨードイソフタル酸等の各種有機沃素化合物及び
未反応の一塩化沃素、遊離沃素等の無機沃素化合物が含
有されており、廃液１００ ｄ中に含まれる沃素量は１
．１５６ｇであり、そのうち有機沃素化合物中に含まれ
るものは０．６９３ｇであった。The reaction filtrate and washing liquid were combined to obtain 5500 d of sample waste liquid. This waste liquid contains 5-amino-2-iodoisophthalic acid, S-amino-4-iodoisophthalic acid, 5-amino-2,4-short isophthalic acid, 5-amino-4-iodoisophthalic acid,
, 6-short isophthalic acid, 5-amino-2,4,6
- Contains various organic iodine compounds such as doryiodoisophthalic acid and inorganic iodine compounds such as unreacted iodine monochloride and free iodine, and the amount of iodine contained in 100 d of waste liquid is 1
．． The amount was 156 g, of which 0.693 g was contained in the organic iodine compound.
上記により得た廃Ｗ５００ ｄを隔膜（カチオン交換膜
、商品名：セレミオンＣＭＶ、旭硝子■製）で隔てられ
た電解槽の陰極室へ入れ、陽極室には１０重量％硫酸５
００ ｄを入れた。陰極材料としてニッケル、陽極材料
として白金を用いて３０°Ｃで定電流電解（０，５Ａ／
ｄａ”）を行い、６Ｆ１モル通電し、還元膜沃素化を行
った。The waste W500 d obtained above was put into the cathode chamber of an electrolytic cell separated by a diaphragm (cation exchange membrane, product name: Selemion CMV, manufactured by Asahi Glass), and the anode chamber was filled with 10% by weight sulfuric acid 5.
I put in 00 d. Constant current electrolysis (0.5A/
da"), and a current of 1 mol of 6F was applied to perform reduced film iodination.
電解液を空気導入管及び排気管を付けた１２反応器に移
し、有効塩素量５％の次亜塩素酸す） ＩＪウム水溶液
にて酸化し沃素を遊離した。The electrolytic solution was transferred to a reactor 12 equipped with an air inlet pipe and an exhaust pipe, and oxidized with an aqueous solution of hypochlorous acid containing 5% effective chlorine to liberate iodine.
次いで、空気を導入し、排気管を１０重量％水酸化ナト
リウム水溶液へと導くことにより遊離した沃素をアルカ
リ溶液に吸収させた。この吸収液中には、沃素として５
．４６ｇ含まれており、廃液中からの沃素回収率は９４
．５％であった。Next, air was introduced and the exhaust pipe was led to a 10% by weight aqueous sodium hydroxide solution to absorb the liberated iodine into the alkaline solution. This absorption liquid contains 5 as iodine.
．． Contains 46g, and the recovery rate of iodine from waste liquid is 94.
．． It was 5%.
実施例２
試料廃液として、ジアドリゾ酸の精製時に生じた廃液を
用いた。Example 2 A waste liquid generated during purification of diadorizoic acid was used as a sample waste liquid.
粗ジアドリゾ酸のナトリウム塩１００ｇを水：イソプロ
パツール＝４０ ： ６０の混合溶媒４００−で再結晶
した。100 g of the crude sodium salt of diadrizoic acid was recrystallized from a mixed solvent of 40:60 water and isopropanol.
得られた濾液及び洗浄液を合わせ、減圧下にイソプロパ
ツールを留去し、残部を水で５００ ｄに希釈し試料廃
液とした。The obtained filtrate and washing solution were combined, and the isopropanol was distilled off under reduced pressure, and the remainder was diluted with water to a concentration of 500 d to provide a sample waste solution.
この廃液中に含まれる沃素量は、１００ｄ当り１．８４
０ｇであった。The amount of iodine contained in this waste liquid is 1.84 per 100 d.
It was 0g.
上記で得た廃液５００ ｄを硫酸でＰＨを１に調整した
のち、実施例１と同様に処理を行い、沃素８．７４ｇを
得た。沃素収率は９５．０％であった。The pH of 500 d of the waste liquid obtained above was adjusted to 1 with sulfuric acid, and then treated in the same manner as in Example 1 to obtain 8.74 g of iodine. The iodine yield was 95.0%.
実施例３
１０重量％硫酸水？８液の代わりに１０重量％硫酸メタ
ノール溶液、ニッケルの代わりに鉛、白金の代わりに鉛
を用い、実施例１と同様の操作を行い、沃素５−２８ｇ
を得た。沃素回収率９１．３％であった。Example 3 10% by weight sulfuric acid water? The same operation as in Example 1 was carried out using a 10% by weight sulfuric acid methanol solution instead of the 8 solution, lead instead of nickel, and lead instead of platinum, and 5-28 g of iodine was obtained.
I got it. The iodine recovery rate was 91.3%.
［発明の効果］
本発明の方法によれば、有機沃素化合物を含有する廃液
から極めて高収率で沃素を回収することができる。また
、回収装置の構成材料の選択及び設計が、公知の回収方
法よりも容易であり、有機沃素化合物を含有する廃液か
ら沃素を回収する方法として工業的に極めて有用である
。[Effects of the Invention] According to the method of the present invention, iodine can be recovered in extremely high yield from waste liquid containing organic iodine compounds. In addition, selection and design of the constituent materials of the recovery device are easier than in known recovery methods, and the present invention is extremely useful industrially as a method for recovering iodine from waste liquid containing organic iodine compounds.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
、酸化し沃素を遊離せしめることを特徴とする沃素の回
収方法。1. A method for recovering iodine, which comprises electrolytically reducing a waste solution containing an organic iodine compound and then oxidizing it to liberate iodine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63048733A JP2569110B2 (en) | 1988-03-03 | 1988-03-03 | Method for recovering iodine from waste liquid containing organic iodine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63048733A JP2569110B2 (en) | 1988-03-03 | 1988-03-03 | Method for recovering iodine from waste liquid containing organic iodine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01224202A true JPH01224202A (en) | 1989-09-07 |
| JP2569110B2 JP2569110B2 (en) | 1997-01-08 |
Family
ID=12811489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63048733A Expired - Fee Related JP2569110B2 (en) | 1988-03-03 | 1988-03-03 | Method for recovering iodine from waste liquid containing organic iodine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2569110B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002008492A1 (en) * | 2000-07-21 | 2002-01-31 | Iodine Technologies Australia Pty Ltd | Process and method for recovery of halogens |
| JP2010236008A (en) * | 2009-03-31 | 2010-10-21 | Daikin Ind Ltd | Oxidation-precipitation method of iodine |
| JP2011527937A (en) * | 2008-07-15 | 2011-11-10 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | Industrial wastewater treatment |
| CN112551733A (en) * | 2020-11-03 | 2021-03-26 | 浙江海拓环境技术有限公司 | Device and method for treating hypophosphite in chemical nickel plating waste liquid |
| CN112778151A (en) * | 2021-03-03 | 2021-05-11 | 浙江司太立制药股份有限公司 | Preparation method of 5-amino-2, 4, 6-triiodo-1, 3-phthalic acid impurity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS631448A (en) * | 1986-05-19 | 1988-01-06 | デルフアイ リサ−チ インコ−ポレイテイツド | Treatment of organic waste and catalyst/promotor compositiontherefor |
-
1988
- 1988-03-03 JP JP63048733A patent/JP2569110B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS631448A (en) * | 1986-05-19 | 1988-01-06 | デルフアイ リサ−チ インコ−ポレイテイツド | Treatment of organic waste and catalyst/promotor compositiontherefor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002008492A1 (en) * | 2000-07-21 | 2002-01-31 | Iodine Technologies Australia Pty Ltd | Process and method for recovery of halogens |
| JP2011527937A (en) * | 2008-07-15 | 2011-11-10 | インドゥストリエ・デ・ノラ・ソチエタ・ペル・アツィオーニ | Industrial wastewater treatment |
| JP2010236008A (en) * | 2009-03-31 | 2010-10-21 | Daikin Ind Ltd | Oxidation-precipitation method of iodine |
| CN112551733A (en) * | 2020-11-03 | 2021-03-26 | 浙江海拓环境技术有限公司 | Device and method for treating hypophosphite in chemical nickel plating waste liquid |
| CN112551733B (en) * | 2020-11-03 | 2022-07-12 | 浙江海拓环境技术有限公司 | Device and method for treating hypophosphite in chemical nickel plating waste liquid |
| CN112778151A (en) * | 2021-03-03 | 2021-05-11 | 浙江司太立制药股份有限公司 | Preparation method of 5-amino-2, 4, 6-triiodo-1, 3-phthalic acid impurity |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2569110B2 (en) | 1997-01-08 |
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