JP3272859B2 - Control method for catalytic wet oxidizer in treatment of wastewater containing ammonia nitrogen - Google Patents
Control method for catalytic wet oxidizer in treatment of wastewater containing ammonia nitrogenInfo
- Publication number
- JP3272859B2 JP3272859B2 JP05912794A JP5912794A JP3272859B2 JP 3272859 B2 JP3272859 B2 JP 3272859B2 JP 05912794 A JP05912794 A JP 05912794A JP 5912794 A JP5912794 A JP 5912794A JP 3272859 B2 JP3272859 B2 JP 3272859B2
- Authority
- JP
- Japan
- Prior art keywords
- concentration
- oxygen
- ion concentration
- treated water
- treatment
- 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.)
- Expired - Fee Related
Links
- 239000002351 wastewater Substances 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 26
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims description 25
- 230000003197 catalytic effect Effects 0.000 title claims description 22
- 239000007800 oxidant agent Substances 0.000 title description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 97
- 239000001301 oxygen Substances 0.000 claims description 97
- 229910052760 oxygen Inorganic materials 0.000 claims description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 229910001868 water Inorganic materials 0.000 claims description 73
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 49
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 39
- 238000009279 wet oxidation reaction Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 239000003054 catalyst Substances 0.000 description 24
- -1 nitrogen-containing ions Chemical class 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000012545 processing Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004817 gas chromatography Methods 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
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アンモニア態窒素を含
む排水を固体触媒の存在下に湿式酸化処理することによ
り、排水中の含有物質を窒素、炭酸ガス、水および灰分
に転換せしめて排水の無害化を行う方法に関する。さら
に詳しくは、本発明は産業排水などに代表されるアンモ
ニア態窒素を含有する種々の排水を、固体触媒の存在
下、かつ酸素含有ガスの存在下に、１００〜３７０℃の
温度および排水が液相を保持する圧力条件下において排
水を湿式酸化処理することにより、排水中の含有物質を
窒素、炭酸ガス、水および灰分に転換せしめて排水の無
害化を行う方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a wastewater containing ammonia nitrogen, which is subjected to wet oxidation in the presence of a solid catalyst to convert substances contained in the wastewater into nitrogen, carbon dioxide, water and ash. And a method for detoxifying the waste. More specifically, the present invention relates to a method in which various wastewaters containing ammonia nitrogen represented by industrial wastewater and the like are treated in the presence of a solid catalyst and an oxygen-containing gas at a temperature of 100 to 370 ° C. The present invention relates to a method for detoxifying wastewater by subjecting wastewater to wet oxidation treatment under pressure conditions that maintain a phase, thereby converting substances contained in the wastewater to nitrogen, carbon dioxide, water, and ash.
【０００２】[0002]
【従来の技術】海域、湖沼、河川などにおいて、富栄養
化によって赤潮が発生したりかび臭物質が発生すること
が問題となって久しいが、この原因は該水域に排出され
る排水中に含有されている窒素、リンなどの栄養塩類が
原因とされている。このため、窒素、リンに関する排水
規制が実施されており、従来の活性汚泥法による二次処
理を行うのみではこれら栄養塩類を十分に処理できない
ために、脱窒工程を新規に設ける必要がある。2. Description of the Related Art In marine areas, lakes, marshes, rivers, etc., it has been a long time since eutrophication caused red tides and musty odor substances, which are contained in wastewater discharged into the waters. It is caused by nutrients such as nitrogen and phosphorus. For this reason, wastewater regulations on nitrogen and phosphorus are being implemented, and these secondary nutrients cannot be sufficiently treated only by secondary treatment by the conventional activated sludge method. Therefore, it is necessary to newly provide a denitrification step.
【０００３】従来、窒素を除く方法としては生物による
脱窒処理、曝気によるストリッピング法、イオン交換
法、次亜塩素酸やオゾンなどの酸化剤による酸化脱窒な
どの方法が用いられている。生物による脱窒処理は、ア
ンモニア態窒素を硝酸態窒素に硝化した後、硝酸態窒素
を嫌気性処理を行って窒素ガスとする方法であるが、処
理時間を長くとる必要があるために、必然的に装置規模
が大きくなるという問題点を有している。ストリッピン
グ法は、液相中にガスを注入し、溶解しているアンモニ
ア態窒素を気相中に放出する方法であるが、汚染物質が
単に液相から気相へと移行するだけで汚染の根本的な解
決とはならないため、気相中のアンモニアを除去するた
めの何らかの工程が必要となる。イオン交換法では、窒
素含有イオン以外のイオンが多量に含有されているよう
は排水では、イオン交換基材を頻繁に再生する必要があ
るとともにイオン交換基材の耐久性を著しく損なう。ま
た、次亜塩素酸による脱窒法は、近年問題になっている
有機塩素を生成する危険性があり、オゾンによる脱窒法
も触媒として臭素イオンの存在が不可欠となり、いずれ
も酸化剤が多量に必要となってコスト高となる。Conventionally, methods for removing nitrogen include denitrification by living organisms, stripping by aeration, ion exchange, and oxidative denitrification by oxidizing agents such as hypochlorous acid and ozone. Denitrification treatment by living organisms is a method of nitrifying ammonia nitrogen to nitrate nitrogen and then performing anaerobic treatment of nitrate nitrogen to produce nitrogen gas.However, since the treatment time needs to be long, it is inevitable. There is a problem that the apparatus scale becomes large. The stripping method is a method in which gas is injected into the liquid phase and the dissolved ammonia nitrogen is released into the gas phase. Since this is not a fundamental solution, some process for removing ammonia in the gas phase is required. In the ion exchange method, it is necessary to frequently regenerate the ion-exchange base material and waste water, so that the ion-exchange base material contains a large amount of ions other than nitrogen-containing ions. In addition, the denitrification method using hypochlorous acid has a risk of generating organic chlorine, which has recently become a problem. The denitrification method using ozone also requires the presence of bromine ions as a catalyst, and both require a large amount of oxidizing agent. As a result, the cost increases.
【０００４】一方、高濃度の硝酸アンモニウムを含有す
る排水の処理方法として、触媒湿式酸化により処理する
方法が提案されている（特開昭６１−２２２５８５号公
報、特開昭６１−２２２５８６号公報、特開昭６１−２
２２５８７号公報、特開昭６１−２２２５８８号公報、
特開昭６１−２２２５８９号公報、特開昭６１−２４５
８８３号公報、特開昭６１−２４５８８４号公報、特開
昭６１−２５７２９０号公報、特開昭６１−２５７２９
１号公報、特開昭６１−２５７２９２号公報、特開平４
−５９０９４号公報、特開平４−６１９８７号公報、特
開平４−２００６９２号公報、特開平４−２００７９０
号公報）。これらは、特定の触媒の存在下、１００〜３
７０℃の温度かつ排水が液相を保持する圧力条件下にお
いて湿式酸化処理する方法である。On the other hand, as a method of treating wastewater containing a high concentration of ammonium nitrate, a method of treating the wastewater by catalytic wet oxidation has been proposed (JP-A-61-222585, JP-A-61-222586, 61-2
No. 22587, JP-A-61-222588,
JP-A-61-222589, JP-A-61-245
883, JP-A-61-245883, JP-A-61-257290, JP-A-61-25729
No. 1, Japanese Patent Application Laid-Open No. 61-257292,
-59094, JP-A-4-61987, JP-A-4-200692, JP-A-4-200790
No.). These are 100 to 3 in the presence of a specific catalyst.
This is a method of performing wet oxidation treatment at a temperature of 70 ° C. and a pressure condition in which waste water retains a liquid phase.
【０００５】[0005]
【本発明が解決しようとする課題】しかし、本発明者ら
がアンモニア態窒素含有排水の処理を行った際には、排
水濃度の変動や装置自体のふれにより、大きく処理効率
が変動することが認められた。すなわち、触媒湿式酸化
法によりアンモニア態窒素含有排水を処理する際には、
装置条件を排水濃度等に対して常時最適に保持しなけれ
ば、安定した高い処理効率は得られないことが明らかに
なった。However, when the present inventors treat ammonia-nitrogen-containing wastewater, the treatment efficiency may fluctuate greatly due to fluctuations in the concentration of wastewater and shake of the apparatus itself. Admitted. That is, when treating ammonia-nitrogen-containing wastewater by the catalytic wet oxidation method,
It became clear that stable high treatment efficiency could not be obtained unless the equipment conditions were always kept optimally for the concentration of wastewater.
【０００６】しかし、実装置においては排水の濃度は一
定ではなく、常時変動するものである。よって実際に
は、アンモニア態窒素含有排水の処理に際し、装置条件
を常に最適な状態に制御しなければ、安定した十分な窒
素の処理を行うことは不可能である。However, in an actual apparatus, the concentration of waste water is not constant, but always fluctuates. Therefore, in practice, it is impossible to perform a stable and sufficient nitrogen treatment unless the apparatus conditions are always controlled to an optimum state in the treatment of the wastewater containing ammonia nitrogen.
【０００７】[0007]
【課題を解決する手段】これに対し、本発明者らは鋭意
研究を重ねた結果、触媒湿式酸化法によりアンモニア態
窒素含有排水を処理するにあたり、窒素の処理効率に対
して装置内に供給する酸素量の影響が非常に大きいこと
を見い出した。すなわち、使用する触媒の種類によって
処理水中に存在するアンモニウムイオンおよび硝酸イオ
ンの濃度は異なるが、アンモニア態窒素含有排水を触媒
湿式酸化法により処理する場合にはどのような触媒を用
いた場合においても図１に示した概念図のとおり、供給
酸素量が少ない場合には、アンモニア態窒素は酸化され
ずに処理水中に残留することになり、また供給酸素量が
過剰になった際には、アンモニア態窒素が硝酸態窒素に
変換されて高濃度で処理水中に存在し、処理水中の全窒
素濃度としては充分な処理を行うことができないことを
見い出した。On the other hand, the inventors of the present invention have conducted intensive studies, and as a result, when treating wastewater containing ammonia nitrogen by the catalytic wet oxidation method, supply the nitrogen into the apparatus with respect to the treatment efficiency of nitrogen. The effect of oxygen content was found to be very large. That is, the concentration of ammonium ion and nitrate ion present in the treated water varies depending on the type of the catalyst used, but no matter what kind of catalyst is used when the wastewater containing ammonia nitrogen is treated by the catalytic wet oxidation method. As shown in the conceptual diagram of FIG. 1, when the supplied oxygen amount is small, the ammonia nitrogen remains in the treated water without being oxidized, and when the supplied oxygen amount becomes excessive, It has been found that nitrogen is converted to nitrate nitrogen and is present in the treated water at a high concentration, so that sufficient treatment cannot be performed as the total nitrogen concentration in the treated water.
【０００８】さらに、アンモニア態窒素含有排水を触媒
湿式酸化処理するに際し、触媒湿式酸化装置より排出さ
れる処理水中のアンモニウムイオン濃度、および硝酸イ
オン濃度が供給酸素の量を判断する指標となることを見
い出し、この測定値を一定の濃度値以下に制御するよう
に装置内に流入させる酸素含有ガス量を制御することに
より、簡便かつ排水の濃度の変動の影響を最小限に抑
え、安定した処理を行うことが可能であることを見い出
した。また、アンモニア態窒素含有排水を触媒湿式酸化
処理するに際し、触媒湿式酸化装置より排出される処理
水中のアンモニウムイオン濃度、硝酸イオン濃度ととも
にガス中の酸素濃度が供給酸素の量を判断する指標とな
ることを見い出し、これらの測定値によって、装置内に
流入させる酸素含有ガス量を制御することにより、簡便
かつ排水の濃度の変動の影響を最小限に抑え、安定した
処理を行うことが可能であることを見い出した。本発明
は、これらの知見を基に完成されたものである。[0008] Further, in performing catalytic wet oxidation treatment of ammonia-nitrogen-containing wastewater, the ammonium ion concentration and nitrate ion concentration in the treated water discharged from the catalytic wet oxidation device are used as indices for judging the amount of supplied oxygen. By controlling the amount of oxygen-containing gas that flows into the apparatus so that this measured value is controlled to a certain concentration value or less, it is simple and minimizes the effect of fluctuations in the concentration of wastewater, and stable processing is achieved. Has found that it is possible to do so. In addition, when the ammonia nitrogen-containing wastewater is subjected to catalytic wet oxidation treatment, the oxygen concentration in the gas together with the ammonium ion concentration and nitrate ion concentration in the treated water discharged from the catalytic wet oxidation device is an index for determining the amount of supplied oxygen. By controlling the amount of oxygen-containing gas flowing into the apparatus based on these measured values, it is possible to carry out a stable treatment simply and with minimal effects of fluctuations in the concentration of wastewater. I found something. The present invention has been completed based on these findings.
【０００９】本発明は、アンモニア態窒素を含有する排
水を触媒湿式酸化処理するに当たり、排水の流量、濃度
の変動の影響を最小限に抑制し、安定した処理を行う簡
便かつ最適な制御方法を提供するものである。The present invention provides a simple and optimal control method for performing a stable treatment by minimizing the effects of fluctuations in the flow rate and concentration of the wastewater in the catalytic wet oxidation treatment of wastewater containing ammonia nitrogen. To provide.
【００１０】本発明は、アンモニア態窒素含有排水を触
媒湿式酸化処理するに際し、あらかじめ処理水中のアン
モニウムイオン濃度および硝酸イオン濃度の最大許容濃
度をそれぞれＣ１およびＣ２と設定し、触媒湿式酸化装
置より排出される気液混合流体を気液分離した後、気相
中の酸素濃度、処理水中のアンモニウムイオン濃度およ
び硝酸イオン濃度を測定し、測定された酸素濃度があら
かじめ設定された範囲内または設定された濃度値、アン
モニウムイオン濃度値および硝酸イオン濃度値がそれぞ
れＣ１以下およびＣ２以下となるように、装置内に流入
させる酸素含有ガス量を制御することを特徴とする触媒
湿式酸化装置の制御方法である。In the present invention, the maximum allowable concentrations of ammonium ion concentration and nitrate ion concentration in the treated water are set to C1 and C2, respectively, when the ammonia-nitrogen-containing wastewater is subjected to catalytic wet oxidation treatment, and discharged from the catalytic wet oxidation device. After gas-liquid separation of the gas-liquid mixed fluid to be performed, the oxygen concentration in the gas phase, the ammonium ion concentration and the nitrate ion concentration in the treated water are measured, and the measured oxygen concentration is within a predetermined range or set. A method for controlling a catalytic wet oxidation apparatus, characterized by controlling the amount of an oxygen-containing gas flowing into an apparatus so that a concentration value, an ammonium ion concentration value, and a nitrate ion concentration value become C1 or less and C2 or less, respectively. .
【００１１】触媒湿式酸化装置において、排水濃度の変
動は、反応装置の各部温度、処理水の性状、排ガスの酸
素濃度などに影響を与えてこれらを変動させる。反応装
置の各部温度は、排水の濃度が変動の前後で極端に異な
る場合には顕著に変化が現れるが、通常はその変化は小
さく、制御のために温度差を検出して用いることは困難
である。これに対して処理水中のアンモニウムイオン濃
度、硝酸イオン濃度、排ガス中の酸素濃度は、装置内の
酸化状況を如実に示す指標となる。In the catalytic wet oxidizer, fluctuations in the concentration of waste water affect the temperature of each part of the reactor, the properties of the treated water, the oxygen concentration of the exhaust gas, and the like. The temperature of each part of the reactor changes remarkably when the concentration of the wastewater is extremely different before and after the fluctuation, but the change is usually small, and it is difficult to detect and use the temperature difference for control. is there. On the other hand, the concentration of ammonium ion and nitrate ion in the treated water and the concentration of oxygen in the exhaust gas are indices that clearly indicate the oxidation state in the apparatus.
【００１２】本発明においては、図２に示すように、あ
らかじめ処理水中のアンモニウムイオン濃度および硝酸
イオン濃度の最大許容濃度を設定し、設定された濃度値
以下におさまるように供給酸素量を増減させる。処理水
中のアンモニウムイオン濃度が高くなるにつれて供給酸
素量を増加させ、また処理水中の硝酸イオン濃度が高く
なるにつれて供給酸素量を減少させることにより制御を
行う。すなわち、処理水中のアンモニウムイオン濃度お
よび硝酸イオン濃度について、その最大許容濃度をそれ
ぞれＣ1、Ｃ2と設定し、アンモニウムイオン濃度がＣ1
以下および硝酸イオン濃度がＣ2以下となるように供給
酸素量を制御することにより安定した処理が行われるの
である。なお、処理水中のアンモニウムイオン濃度およ
び硝酸イオン濃度の最大許容濃度ではなく、最適な濃度
の範囲を設定することは、得られる効果は最大許容濃度
を設定する場合と同様であり、設定値が増えるのみであ
るために好ましくない。In the present invention, as shown in FIG. 2, the maximum allowable concentrations of the ammonium ion concentration and the nitrate ion concentration in the treated water are set in advance, and the supplied oxygen amount is increased or decreased so as to fall below the set concentration values. . The control is performed by increasing the supplied oxygen amount as the ammonium ion concentration in the treated water increases, and decreasing the supplied oxygen amount as the nitrate ion concentration in the treated water increases. That is, the maximum allowable concentrations of the ammonium ion concentration and the nitrate ion concentration in the treated water are set to C1 and C2, respectively, and the ammonium ion concentration is set to C1 and C2.
By controlling the amount of supplied oxygen so that the concentration of nitrate ions is equal to or less than C2, stable processing can be performed. In addition, setting the optimum concentration range, not the maximum allowable concentration of ammonium ion concentration and nitrate ion concentration in the treatment water, is the same as the effect obtained when setting the maximum allowable concentration, and the set values increase. It is not preferable because it is only.
【００１３】供給酸素量の制御方法としては、最大許容
濃度を逸脱した際にその逸脱量に応じて供給酸素量を変
化させる、測定された濃度値に応じて供給酸素量を変化
させる、その両者を組み合わせて供給酸素量を変化させ
るなどの一般的な方法が用いられる。また、偏差に応じ
て供給酸素量を変化させる場合には、その変化量は段階
的、比例的、二次曲線的など、通常に用いられている手
法で変化量を決定することができる。As a control method of the supplied oxygen amount, when the concentration deviates from the maximum allowable concentration, the supplied oxygen amount is changed according to the deviation amount, and the supplied oxygen amount is changed according to the measured concentration value. And a general method of changing the supply oxygen amount. When the supply oxygen amount is changed according to the deviation, the change amount can be determined by a commonly used method such as stepwise, proportional, or quadratic curve.
【００１４】処理水中のアンモニウムイオン濃度ととも
に硝酸イオン濃度を検出し、検出されたアンモニウムイ
オン濃度、硝酸イオン濃度によって供給酸素量を制御す
ることにより、処理水中のアンモニウムイオン濃度を測
定して供給酸素量不足の場合の検出を的確かつ微量の不
足の場合まで行い、処理水中の硝酸イオン濃度を測定し
て供給酸素量過多の場合の検出を的確かつ微量の過多の
場合まで行うことになり、アンモニウムイオン単独また
は硝酸イオン単独による制御の場合よりも、より高効率
で安定した処理が可能となるのである。[0014] The ammonium ion concentration in the treated water is measured by detecting the ammonium ion concentration in the treated water and the nitrate ion concentration, and controlling the supplied oxygen amount based on the detected ammonium ion concentration and nitrate ion concentration. Insufficient detection will be performed even if the amount is insufficient, and the concentration of nitrate ions in the treated water will be measured. Higher efficiency and stable processing can be achieved as compared with the case of controlling by solely or by nitrate ion alone.
【００１５】処理水中のアンモニウムイオン濃度および
硝酸イオン濃度の最大許容濃度を定めることにより、供
給酸素量の必要酸素量に対する増加および減少を検出す
ることが可能になり、供給酸素量を制御して適正な処理
を行うことが可能となる。処理水中のアンモニウムイオ
ン濃度または硝酸イオン濃度のいずれかの最大許容濃度
を定めず、処理水中のアンモニウムイオン濃度の最大値
のみを定めてその値を超えないように供給酸素量を制御
する、もしくは処理水中の硝酸イオン濃度の最大値のみ
を定めてその値を超えないように供給酸素量を制御する
ことによって適正な処理は行えない。すなわち、処理水
中のアンモニウムイオン濃度の最大値のみを定めてその
値を超えないように供給酸素量を制御することは、供給
酸素量の過少現象は検出できるが過剰現象を検出するこ
とは不可能であり、供給酸素量が大過剰となって処理水
中に硝酸イオンが存在する場合がある。また、処理水中
の硝酸イオン濃度の最大値のみを定めてその値を超えな
いように供給酸素量を制御することは、供給酸素量の過
剰現象は検出できるが過少現象を検出することは不可能
であり、供給酸素量が不足して処理水中にアンモニウム
イオンが存在する場合がある。By determining the maximum allowable concentrations of ammonium ion and nitrate ion in the treated water, it is possible to detect an increase or decrease in the amount of supplied oxygen with respect to the required amount of oxygen. Processing can be performed. The maximum allowable concentration of either the ammonium ion concentration or the nitrate ion concentration in the treated water is not determined, and only the maximum value of the ammonium ion concentration in the treated water is determined and the supplied oxygen amount is controlled so as not to exceed the value. Proper processing cannot be performed by determining only the maximum value of the nitrate ion concentration in water and controlling the supplied oxygen amount so as not to exceed the maximum value. In other words, by determining only the maximum value of the concentration of ammonium ions in the treated water and controlling the amount of supplied oxygen so as not to exceed the maximum value, it is possible to detect the phenomenon of insufficient supply of oxygen but not to detect the excess phenomenon. In some cases, the amount of supplied oxygen becomes so large that nitrate ions are present in the treated water. In addition, if only the maximum value of the nitrate ion concentration in the treated water is determined and the supplied oxygen amount is controlled so as not to exceed that value, an excess phenomenon of the supplied oxygen amount can be detected, but an insufficient phenomenon cannot be detected. In some cases, the amount of supplied oxygen is insufficient and ammonium ions are present in the treated water.
【００１６】処理水中のアンモニウム濃度および硝酸イ
オン濃度の最大許容濃度は、排水中のアンモニア態窒素
の濃度、要求される処理効率、使用する触媒の種類によ
って大きく異なるが、通常は要求される処理水質以下の
条件下で設定する。要求される処理水質以上の濃度を最
適な範囲または濃度値とした場合には、要求される処理
効率が得られていない場合でも処理効率を高くするよう
な供給酸素量の制御が行われない。処理水中のアンモニ
ウムイオン濃度および硝酸イオン濃度の最大許容濃度
は、低いほど全窒素処理効率が高くなる。一例を挙げれ
ば、後述する触媒調製例において調製した鉄−ジルコニ
ウム−パラジウム系触媒を使用し、排水中のアンモニア
態窒素濃度が１，５００ｍｇ／ｌ、要求される処理水中
の全窒素濃度が１０ｍｇ／ｌ以下の場合、処理水中のア
ンモニウムイオン濃度の最大許容濃度は８ｍｇ／ｌ、好
ましくは５ｍｇ／ｌ、処理水中の硝酸イオン濃度の最大
許容濃度は８ｍｇ／ｌ、好ましくは５ｍｇ／ｌとして供
給酸素量の制御を行う。The maximum allowable concentrations of ammonium and nitrate ions in the treated water vary greatly depending on the concentration of ammonia nitrogen in the waste water, the required treatment efficiency, and the type of catalyst used. Set under the following conditions. When the concentration equal to or higher than the required treatment water quality is set to the optimum range or concentration value, even if the required treatment efficiency is not obtained, the supply oxygen amount is not controlled to increase the treatment efficiency. The lower the maximum allowable concentration of ammonium ion concentration and nitrate ion concentration in the treatment water, the higher the total nitrogen treatment efficiency. As an example, using an iron-zirconium-palladium catalyst prepared in a catalyst preparation example described below, the concentration of ammonia nitrogen in wastewater is 1,500 mg / l, and the required total nitrogen concentration in treated water is 10 mg / l. l or less, the maximum allowable concentration of ammonium ion in the treated water is 8 mg / l, preferably 5 mg / l, and the maximum allowable concentration of nitrate ion in the treated water is 8 mg / l, preferably 5 mg / l. Control.
【００１７】さらに本発明は、処理水中のアンモニウム
イオン濃度、硝酸イオン濃度とともに排ガス中の酸素濃
度を検出し、検出されたアンモニウムイオン濃度、硝酸
イオン濃度および酸素濃度によって供給酸素量を制御す
ることが好ましい。排ガスの酸素濃度を測定し、供給酸
素量の制御に反映させることによって、被処理水の濃度
変動を、処理水中のアンモニウムイオン濃度と硝酸イオ
ン濃度による制御の場合よりもタイムラグが短くするこ
とができ、急激な濃度変動にも対応した処理を行うこと
が可能となる。また、処理水中のアンモニウムイオン濃
度、硝酸イオン濃度とともに排ガス中の酸素濃度を検出
し、検出されたアンモニウムイオン濃度、硝酸イオン濃
度および酸素濃度によって供給酸素量を制御することに
より、排ガス中の酸素濃度単独による制御よりも処理水
の性状を正確に把握することが可能となり、より高効率
な処理が可能となる。Further, the present invention detects the oxygen concentration in the exhaust gas together with the ammonium ion concentration and the nitrate ion concentration in the treated water, and controls the supplied oxygen amount based on the detected ammonium ion concentration, nitrate ion concentration and oxygen concentration. preferable. By measuring the oxygen concentration of the exhaust gas and reflecting it in the control of the amount of supplied oxygen, the time lag of the concentration fluctuation of the water to be treated can be made shorter than in the case of control using the ammonium ion concentration and nitrate ion concentration in the treatment water. In addition, it is possible to perform processing corresponding to a rapid change in density. In addition, the oxygen concentration in the exhaust gas is detected by detecting the oxygen concentration in the exhaust gas together with the ammonium ion concentration and the nitrate ion concentration in the treated water, and controlling the supplied oxygen amount based on the detected ammonium ion concentration, the nitrate ion concentration, and the oxygen concentration. It becomes possible to accurately grasp the properties of the treated water as compared with the case where the control is performed alone, and it is possible to perform the treatment with higher efficiency.
【００１８】処理水中のアンモニウムイオン濃度、硝酸
イオン濃度および排ガスの酸素濃度を併用して供給酸素
量を制御する場合にも、処理水中のアンモニウムイオン
濃度および硝酸イオン濃度については、あらかじめアン
モニウムイオン濃度および硝酸イオン濃度の最大許容濃
度を要求されている処理水質以下に設定し、処理水中の
アンモニウムイオン濃度および硝酸イオン濃度が最大許
容濃度を超えないように供給酸素量の制御を行えばよ
い。In the case where the supplied oxygen amount is controlled by using the ammonium ion concentration, the nitrate ion concentration in the treated water and the oxygen concentration of the exhaust gas together, the ammonium ion concentration and the nitrate ion concentration in the treated water are determined in advance. The maximum allowable concentration of the nitrate ion concentration may be set to be equal to or lower than the required treatment water quality, and the supplied oxygen amount may be controlled so that the ammonium ion concentration and the nitrate ion concentration in the treatment water do not exceed the maximum allowable concentrations.
【００１９】処理水中のアンモニウムイオン濃度、硝酸
イオン濃度と排ガスの酸素濃度を併用して供給酸素量を
制御する場合には、排ガス中の酸素濃度については、あ
らかじめ排ガス中の酸素濃度の最適な範囲を、酸素濃度
計の検出限界以上で上限値と下限値を設定し、その範囲
内におさまるように供給酸素ガス量を増減させればよ
い。排ガス中の酸素濃度の最適な範囲を定めることによ
り、供給酸素量の状況を迅速に把握し、急激な濃度変動
によって処理水中にアンモニウムイオンまたは硝酸イオ
ンが高濃度で存在することを防止する。なお、制御は排
ガス中の酸素濃度が高くなるにつれて供給酸素量を減少
させ、排ガス中の酸素濃度が低くなるにつれて供給酸素
量を増加させることにより行う。設定する酸素濃度の最
適な範囲は、要求されている処理水質、使用する触媒、
および使用する酸素含有ガス中の酸素濃度によって大き
く異なるが、一例を挙げれば、後述する触媒調製例にお
いて調製した鉄−ジルコニウム−パラジウム系触媒を使
用し、酸素含有ガスとして空気を用い、排水中のアンモ
ニア態窒素濃度が１，５００ｍｇ／ｌ、要求される処理
水中の全窒素濃度が２０ｍｇ／ｌ以下の場合、０.５〜
２vol%となる。なお、排ガス中の酸素濃度の最適な範囲
については、最大値のみを設定してそれを超えないよう
に、または最小値のみを設定してそれを下回らないよう
に供給酸素量の制御を行ってもよい。ただしこれらの場
合には、供給酸素量の過少現象または過剰現象の一方に
ついては、短いタイムラグで検出できないことになるた
め、アンモニウムイオンが検出されることは許容されて
も硝酸イオンが検出されることは許されない、あるいは
硝酸イオンが検出されることは許容されてもアンモニウ
ムイオンが検出されることは許されないなどの場合に有
効である。When the supplied oxygen amount is controlled by using the ammonium ion concentration and the nitrate ion concentration in the treated water in combination with the oxygen concentration of the exhaust gas, the oxygen concentration in the exhaust gas is determined in advance in the optimum range of the oxygen concentration in the exhaust gas. The upper limit value and the lower limit value may be set above the detection limit of the oximeter, and the supplied oxygen gas amount may be increased or decreased so as to fall within the range. By determining the optimum range of the oxygen concentration in the exhaust gas, the situation of the supplied oxygen amount is quickly grasped, and the presence of a high concentration of ammonium ions or nitrate ions in the treated water due to rapid concentration fluctuation is prevented. The control is performed by decreasing the supplied oxygen amount as the oxygen concentration in the exhaust gas increases, and increasing the supplied oxygen amount as the oxygen concentration in the exhaust gas decreases. The optimal range of the oxygen concentration to be set depends on the required treatment water quality, the catalyst used,
Although it greatly varies depending on the oxygen concentration in the oxygen-containing gas used, for example, an iron-zirconium-palladium-based catalyst prepared in a catalyst preparation example described below is used, and air is used as the oxygen-containing gas. If the ammonia nitrogen concentration is 1,500 mg / l and the required total nitrogen concentration in the treated water is 20 mg / l or less,
2 vol%. For the optimal range of the oxygen concentration in the exhaust gas, set the maximum value only and do not exceed it, or set only the minimum value and control the supplied oxygen amount so as not to fall below it. Is also good. However, in these cases, it will not be possible to detect either a shortage phenomenon or an excessive phenomenon of the amount of supplied oxygen with a short time lag. This is effective in cases such as where the detection of nitrate ions is permitted or the detection of ammonium ions is not permitted.
【００２０】本発明における酸素含有ガスとは酸素を含
有する気体のことであり、具体的には空気、酸素富化空
気、酸素を含有する排ガスなど、種々のものを挙げるこ
とができる。酸素含有ガス中の酸素濃度としては、３vo
l%以上、好ましくは５vol%以上である。酸素含有ガス中
の酸素濃度が３vol%以下では、処理後の排ガス中の酸素
濃度が低くなりすぎて酸素濃度計による測定値の信頼度
が低くなり、供給酸素量の過剰または過少の検出力が低
下し、供給酸素量の制御が正確に行われなくなって安定
した処理を行えない場合がある。なお、上記酸素濃度は
いずれもドライベースであり、水蒸気を分離した状態で
の濃度値であるため、水蒸気を分離せずに測定を行う場
合には水蒸気による誤差を補正して制御値を決定すれば
よい。The oxygen-containing gas in the present invention is a gas containing oxygen, and specific examples thereof include air, oxygen-enriched air, and exhaust gas containing oxygen. The oxygen concentration in the oxygen-containing gas is 3 vo
l% or more, preferably 5 vol% or more. When the oxygen concentration in the oxygen-containing gas is 3 vol% or less, the oxygen concentration in the exhaust gas after treatment becomes too low, and the reliability of the measurement value obtained by the oximeter becomes low. In some cases, the amount of oxygen supplied decreases, and the control of the supplied oxygen amount cannot be performed accurately, so that stable processing cannot be performed. In addition, since the above oxygen concentrations are all on a dry basis and are concentration values in a state where water vapor is separated, when performing measurement without separating water vapor, it is necessary to correct an error due to water vapor to determine a control value. I just need.
【００２１】本発明において、酸素含有ガスは連続的に
装置内に導入され、排水の処理に使用されることにな
る。間欠的に導入された場合には排水に無酸素状態の部
分が現れて処理が行われなくなり、結果として処理効率
が低くなる可能性があるため好ましくない。In the present invention, the oxygen-containing gas is continuously introduced into the apparatus and used for treating wastewater. When introduced intermittently, anoxic portions appear in the wastewater, and the treatment is not performed. As a result, there is a possibility that the treatment efficiency is lowered, which is not preferable.
【００２２】本発明におけるアンモニア態窒素とは、液
相中に溶解しているアンモニアおよびアンモニウムイオ
ンとなっているものの総称を意味し、一例を挙げれば硫
酸アンモニウム、塩化アンモニウムなどの溶解塩類、ア
ンモニア水などが挙げられるが、これらに限定されるも
のではない。In the present invention, the term "ammonia nitrogen" is a general term for ammonia and ammonium ions dissolved in a liquid phase. For example, dissolved salts such as ammonium sulfate and ammonium chloride, aqueous ammonia, etc. But are not limited to these.
【００２３】本発明において、処理対象となる排水中の
アンモニア態窒素の濃度としては、水溶液中に溶解して
いるものであれば、範囲は限定されない。In the present invention, the concentration of ammonia nitrogen in the wastewater to be treated is not limited as long as it is dissolved in an aqueous solution.
【００２４】本発明において用いられる触媒は、湿式酸
化反応条件において、耐久性と活性を備えた固体触媒で
あればいずれの触媒を用いてもよいが、一例を挙げれば
触媒成分としてチタン、ケイ素、ジルコニウム、マンガ
ン、鉄、コバルト、ニッケル、タングステン、セリウ
ム、銅、銀、金、白金、パラジウム、ロジウム、ルテニ
ウム、およびイリジウムよりなる群より選ばれた少なく
とも１種の元素の水に不溶性または難溶性の化合物を含
有してなる固体触媒である。さらに、触媒Ａ成分として
マンガン、鉄、コバルトよりなる群より選ばれた少なく
とも１種の元素の水に不溶性または難溶性の化合物、触
媒Ｂ成分としてチタン、ケイ素、およびジルコニウムよ
りなる群より選ばれた少なくとも１種の元素の水に不溶
性または難溶性の化合物、および触媒Ｃ成分としてセリ
ウム、タングステン、銅、銀、金、白金、パラジウム、
ロジウム、ルテニウム、およびイリジウムよりなる群よ
り選ばれた少なくとも１種の元素の水に不溶性または難
溶性の化合物を含有してなる固体触媒を用いることが好
ましい。該触媒における各触媒成分の比率は、Ａ成分が
酸化物の形で２０〜９８．９重量％、Ｂ成分は酸化物の
形で１〜８０重量％、Ｃ成分は金属もしくは化合物の形
で０．１〜２０重量％の範囲が適当である。好ましく
は、Ａ成分が酸化物の形で４０〜９５重量％、Ｂ成分は
酸化物の形で５〜６０重量％、Ｃ成分は金属もしくは化
合物の形で０．１〜１５重量％の範囲である。Ａ成分が
上記範囲外では触媒活性が不十分であり、またＣ成分に
ついても同様に上記範囲を下回る場合には触媒活性が不
十分となり、また白金、パラジウムおよびロジウムなど
の貴金属の場合、上記範囲を上回る場合には原料コスト
が高くなり相応した十分な効果が期待できない。As the catalyst used in the present invention, any catalyst may be used as long as it is a solid catalyst having durability and activity under wet oxidation reaction conditions. For example, titanium, silicon, At least one element selected from the group consisting of zirconium, manganese, iron, cobalt, nickel, tungsten, cerium, copper, silver, gold, platinum, palladium, rhodium, ruthenium, and iridium, is insoluble or hardly soluble in water. It is a solid catalyst containing a compound. Further, the catalyst A component is selected from the group consisting of manganese, iron, and at least one element insoluble or hardly soluble in water, and the catalyst B component is selected from the group consisting of titanium, silicon, and zirconium. Water-insoluble or hardly soluble compound of at least one element, and cerium, tungsten, copper, silver, gold, platinum, palladium,
It is preferable to use a solid catalyst containing a water-insoluble or hardly soluble compound of at least one element selected from the group consisting of rhodium, ruthenium, and iridium. The ratio of each catalyst component in the catalyst is such that component A is 20 to 98.9% by weight in the form of an oxide, component B is 1 to 80% by weight in the form of an oxide, and component C is 0 to 8% by weight in the form of a metal or a compound. A suitable range is from 0.1 to 20% by weight. Preferably, component A ranges from 40 to 95% by weight in oxide form, component B ranges from 5 to 60% by weight in oxide form, and component C ranges from 0.1 to 15% by weight in metal or compound form. is there. When the component A is out of the above range, the catalytic activity is insufficient. When the component C is also below the above range, the catalytic activity becomes insufficient. In the case of a noble metal such as platinum, palladium and rhodium, the catalytic activity becomes insufficient. If the ratio exceeds, the raw material cost increases, and a correspondingly sufficient effect cannot be expected.
【００２５】本発明で使用する触媒は前記の通り特定さ
れた組成からなるものが好ましく、触媒形状としては、
粒状、ペレット状、およびハニカムなどの一体構造体な
ど種々のものを採用することができる。The catalyst used in the present invention preferably has the composition specified as described above.
Various things such as a granular form, a pellet form, and an integrated structure such as a honeycomb can be adopted.
【００２６】上記の触媒を用いてアンモニア態窒素含有
排水を処理すれば、全窒素処理効率が大幅に上昇するこ
とになる。If the wastewater containing ammonia nitrogen is treated using the above catalyst, the total nitrogen treatment efficiency will be greatly increased.
【００２７】本発明における排水処理時の温度は１００
〜３７０℃、好ましくは１５０℃〜３００℃の範囲内で
ある。排水処理時の温度が１００℃以下ではアンモニア
態窒素の充分な除去を行うことができず、また３７０℃
以上では水の臨界温度を超えることになり、反応装置が
高価になって好ましくない。圧力は処理温度において、
排水が液相を保持する圧力を設定する。湿式酸化反応は
酸素分圧が高いほど反応が速やかに進行するため、処理
時の圧力が高いほど反応が速くなるが、装置圧力が高く
なると装置自体が高価となるために、目標とする処理時
間、処理効率に合わせて適宜設定すればよい。In the present invention, the temperature during wastewater treatment is 100.
370 ° C, preferably 150 ° C to 300 ° C. If the temperature at the time of wastewater treatment is 100 ° C. or less, it is not possible to sufficiently remove ammonia nitrogen.
In the above case, the temperature exceeds the critical temperature of water, and the reactor becomes expensive, which is not preferable. Pressure at processing temperature,
Set the pressure at which the wastewater holds the liquid phase. In the wet oxidation reaction, the higher the oxygen partial pressure, the faster the reaction proceeds.The higher the pressure during the process, the faster the reaction. However, the higher the pressure of the device, the more expensive the device itself. , May be set appropriately according to the processing efficiency.
【００２８】本発明における排水の流入速度は、触媒に
対して空間速度（ＬＨＳＶ）で０.５〜２０／ｈｒの範
囲内であることが好ましい。ＬＨＳＶが０.５／ｈｒ以
下では触媒量に対して処理効率は上昇せずコスト的に高
くなり、好ましくない。ＬＨＳＶが２０／ｈｒ以上では
アンモニア態窒素の処理効率が充分でなく、好ましくな
い。In the present invention, the inflow velocity of the waste water is preferably in the range of 0.5 to 20 / hr in space velocity (LHSV) with respect to the catalyst. If the LHSV is 0.5 / hr or less, the treatment efficiency does not increase with respect to the amount of the catalyst, and the cost becomes high. If the LHSV is 20 / hr or more, the processing efficiency of ammonia nitrogen is insufficient, which is not preferable.
【００２９】本発明における酸素含有ガスの供給量は、
処理を行う間に自動制御されるため、特に限定はされな
い。In the present invention, the supply amount of the oxygen-containing gas is
There is no particular limitation because it is automatically controlled during the processing.
【００３０】本発明において用いれられるアンモニウム
イオン濃度計としては、液相中のアンモニウムイオン濃
度を連続測定し、検出値を出力できる機能のあるもので
あればいずれのものを用いてもよい。検出器としては、
イオンクロマトグラフによる導電量検出、ガスクロマト
グラフによるＦＴＤ、イオン電極など既知の様々なもの
が適用可能である。As the ammonium ion concentration meter used in the present invention, any one can be used as long as it has a function of continuously measuring the concentration of ammonium ion in the liquid phase and outputting a detected value. As a detector,
Various known materials such as conductivity detection by ion chromatography, FTD by gas chromatography, and ion electrodes can be applied.
【００３１】本発明において用いれられる硝酸イオン濃
度計としては、液相中の硝酸イオン濃度を連続測定し、
検出値を出力できる機能のあるものであればいずれのも
のを用いてもよい。検出器としては、イオンクロマトグ
ラフによる導電量検出、ガスクロマトグラフによるＦＴ
Ｄ、イオン電極など既知の様々なものが適用可能であ
る。The nitrate ion concentration meter used in the present invention continuously measures the nitrate ion concentration in the liquid phase,
Any device having a function of outputting a detection value may be used. Detectors include conductivity detection by ion chromatography and FT by gas chromatography.
Various known elements such as D and ion electrodes can be applied.
【００３２】本発明において用いられる酸素濃度計とし
ては、気相中の酸素を連続測定し、検出値を出力できる
機能のあるものであればいずれのものを用いてもよい。
例示すれば、ジルコニア式酸素濃度計、ガルバニ電池式
酸素濃度計、磁気式酸素濃度計など市販のものが用いら
れる。As the oxygen concentration meter used in the present invention, any device can be used as long as it has a function of continuously measuring oxygen in the gas phase and outputting a detected value.
For example, commercially available products such as a zirconia oxygen meter, a galvanic cell oxygen meter, and a magnetic oxygen meter are used.
【００３３】[0033]
【実施例】以下、本発明を実施例にしたがって詳細に説
明するが、本発明はこれらに限定されるものではない。EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
【００３４】（触媒調製例）硝酸第二鉄を水に溶解させ
て硝酸ジルコニル、硝酸パラジウムを添加し、水酸化ナ
トリウム水溶液を加えてｐＨを９とし、これをろ過洗浄
して得られたケーキを乾燥させて７００℃で焼成後、粉
砕して鉄−ジルコニウム−パラジウムの酸化物粉体（重
量比Ｆｅ2Ｏ3：ＺｒＯ2：Ｐｄ＝６０：３９．５：０．
５）を得た。(Catalyst Preparation Example) Ferric nitrate is dissolved in water, zirconyl nitrate and palladium nitrate are added, and an aqueous solution of sodium hydroxide is added to adjust the pH to 9. The resulting cake is filtered and washed to obtain a cake. It is dried, calcined at 700 ° C., and pulverized to obtain an iron-zirconium-palladium oxide powder (weight ratio Fe 2 O 3: ZrO 2: Pd = 60: 39.5: 0.
5) was obtained.
【００３５】かくして得られた酸化物粉体にでんぷん、
水を加えてよく混合した後、ペレット状（円筒形、平均
径５ｍｍ、長さ６ｍｍ）に成型し、乾燥後、４００℃で
４時間焼成して完成触媒を得た。The thus obtained oxide powder is added to starch,
After adding water and mixing well, the mixture was shaped into a pellet (cylindrical, average diameter 5 mm, length 6 mm), dried, and calcined at 400 ° C. for 4 hours to obtain a completed catalyst.
【００３６】 （比較例１） 図３に示すようなフロー
にしたがって、表１に示すような組成よりなる排水を処
理した。まずタンク５より送られてくる排水をポンプ３
で１リットル／ｈｒの流量で７０ｋｇ／ｃｍ２Ｇまで昇
圧して装置内へ供給した。また、１０重量％の炭酸ソー
ダ水溶液をライン１２を通じて１００ｍｌ／ｈｒの流量
でポンプ４により昇圧、供給し、前記排水に混入させ
た。一方、ライン１３より供給される空気をコンプレッ
サー７で昇圧した後、前記混合液に混入した。この気液
混合物をライン１４を経て、熱交換器２およびヒーター
１６において２５０℃に加熱した後、湿式酸化塔１へ導
入した。湿式酸化塔１には触媒調製例で得られた触媒
０．５リットルが充填されており、湿式酸化塔１におい
て排水を処理し、処理水をライン１５を経て熱交換器２
において冷却し、気液分離器６へ流した。気液分離器６
においては、液面コントローラ（ＬＣ）により液面を検
出し、液面制御弁８を作動させて一定の液面を保持する
とともに、圧力コントローラ（ＰＣ）により圧力を検出
して圧力制御弁９を作動させて一定の圧力を保持するよ
うに操作されている。圧力制御弁９より排出されたガス
中の酸素濃度は、酸素濃度計１０により、また処理水の
アンモニウムイオン濃度および硝酸イオン濃度はアンモ
ニウムイオン検出器および硝酸イオン検出器１１により
常時監視されている。 (Comparative Example 1) Wastewater having the composition shown in Table 1 was treated according to the flow shown in FIG. First, drain water sent from tank 5 is pumped
The pressure was increased to 70 kg / cm 2 G at a flow rate of 1 liter / hr and supplied into the apparatus. A 10% by weight aqueous sodium carbonate solution was pressurized and supplied by the pump 4 at a flow rate of 100 ml / hr through the line 12, and was mixed with the wastewater. On the other hand, after the air supplied from the line 13 was pressurized by the compressor 7, it was mixed into the mixed liquid. This gas-liquid mixture was heated to 250 ° C. in the heat exchanger 2 and the heater 16 via the line 14 and then introduced into the wet oxidation tower 1. The wet oxidation tower 1 is filled with 0.5 liter of the catalyst obtained in the catalyst preparation example, the wastewater is treated in the wet oxidation tower 1, and the treated water is passed through a line 15 to a heat exchanger 2.
, And flowed to the gas-liquid separator 6. Gas-liquid separator 6
In, the liquid level is detected by a liquid level controller (LC), the liquid level control valve 8 is operated to maintain a constant liquid level, and the pressure is detected by a pressure controller (PC) to operate the pressure control valve 9. It is operated to maintain a constant pressure when activated. The oxygen concentration in the gas discharged from the pressure control valve 9 is constantly monitored by an oxygen concentration meter 10, and the ammonium ion concentration and the nitrate ion concentration of the treated water are constantly monitored by an ammonium ion detector and a nitrate ion detector 11.
【００３７】アンモニウムイオン濃度計の最大許容濃度
を１ｍｇ／ｌ、硝酸イオン濃度計の最大許容濃度を５ｍ
ｇ／ｌ以下になるように供給ガス量を自動制御し、２４
時間ごとに排水濃度を表１の範囲内で変動させて１００
時間の連続処理テストを行った。The maximum allowable concentration of the ammonium ion concentration meter was 1 mg / l, and the maximum allowable concentration of the nitrate ion concentration meter was 5 m.
g / l or less.
The effluent concentration is changed within the range shown in
A time continuous processing test was performed.
【００３８】排水中のアンモニア濃度、処理水中のアン
モニアおよび硝酸の各濃度の経時変化を図４に示す。な
お、亜硝酸イオンは処理水中には検出されなかった。FIG. 4 shows the time-dependent changes in the concentration of ammonia in the wastewater and the concentrations of ammonia and nitric acid in the treated water. Incidentally, nitrite ions were not detected in the treated water.
【００３９】 （比較例２） 供給空気量を排ガスの酸
素濃度、処理水のアンモニウムイオン濃度および硝酸イ
オン濃度に追随させずに一定とした以外は比較例１と同
様の条件下において処理テストを行った。結果を図５に
示す。なお、亜硝酸イオンは処理水中には検出されなか
った。 (Comparative Example 2) A treatment test was performed under the same conditions as in Comparative Example 1 except that the supplied air amount was kept constant without following the oxygen concentration of the exhaust gas, the ammonium ion concentration and the nitrate ion concentration of the treated water. Was. FIG. 5 shows the results. Incidentally, nitrite ions were not detected in the treated water.
【００４０】 （実施例１） 供給空気量を排ガスの酸
素濃度が０．５〜１ｖｏｌ％の範囲内となるように、処
理水のアンモニウムイオン濃度、硝酸イオン濃度による
制御と併用して供給酸素量を制御した以外は比較例１と
同様の条件下において処理テストを行った。結果を図６
に示す。なお、亜硝酸イオンは処理水中には検出されな
かった。 (Example 1) The supply oxygen amount is controlled in combination with the ammonium ion concentration and nitrate ion concentration of the treated water so that the supply air amount is within the range of 0.5 to 1 vol% of the exhaust gas. The processing test was performed under the same conditions as in Comparative Example 1 except that Fig. 6 shows the results.
Shown in Incidentally, nitrite ions were not detected in the treated water.
【００４１】[0041]
【表１】 [Table 1]
【図１】図１は、触媒湿式酸化法によってアンモニア態
窒素含有排水を処理した場合の供給酸素量と処理水のア
ンモニウムイオン及び硝酸イオンの濃度の関係の概念図
である。FIG. 1 is a conceptual diagram showing the relationship between the amount of supplied oxygen and the concentrations of ammonium ions and nitrate ions in treated water when treating wastewater containing ammonia nitrogen by a catalytic wet oxidation method.
【図２】図２は、処理水中のアンモニウムイオン濃度と
硝酸イオン濃度によって供給酸素量を制御する際の概念
図である。 Ｃ１：処理水中のアンモニウムイオンの最大許容濃度 Ｃ２：処理水中の硝酸イオン濃度の最大許容濃度 ＱＨ：処理水中の硝酸イオン濃度がＣ２の際の供給酸素
量 ＱＬ：処理水中のアンモニウムイオン濃度がＣ１の際の
供給酸素量 Ｑ：処理水中の硝酸イオンがＣの際の供給酸素量FIG. 2 is a conceptual diagram when the supply oxygen amount is controlled by the ammonium ion concentration and the nitrate ion concentration in the treatment water. C1: Maximum allowable concentration of ammonium ion in treated water C2: Maximum allowable concentration of nitrate ion concentration in treated water QH: Supply oxygen amount when nitrate ion concentration in treated water is C2 QL: Ammonium ion concentration in treated water is C1 Of oxygen supply at the time of treatment Q: The amount of oxygen supplied when nitrate ions in the treated water are C
【図３】図３は、本発明に係る好ましい処理装置のフロ
ーを示すものである。 １．触媒湿式酸化反応器 ２．熱交換器 ３．排水フィールドポンプ ４．炭酸ソーダ水溶液フィールドポンプ ５．排水タンク ６．気液分離器 ７．エアーコンプレッサー ８．液面調節弁 ９．圧力調節弁 １０．酸素濃度計 １１．アンモニウイオン濃度計及び硝酸イオン濃度計 １２．炭酸ソーダ水溶液フィールドライン １３．エアーライン １６．電気ヒーターFIG. 3 shows a flow of a preferred processing apparatus according to the present invention. 1. 1. Catalytic wet oxidation reactor Heat exchanger 3. Drainage field pump ４． 4. Aqueous sodium carbonate solution field pump Drain tank 6. 6. Gas-liquid separator 7. Air compressor Liquid level control valve 9. Pressure control valve 10. Oxygen meter 11. Ammonium ion concentration meter and nitrate ion concentration meter 12. Sodium carbonate aqueous solution field line Air line 16. Electric heater
【図４】 比較例１の結果であり、排水中のアンモニウ
ムイオン濃度を２４時間ごとに段階的に変化させ、処理
水中のアンモニウムイオン濃度、硝酸イオン濃度の状況
を示したものである。FIG. 4 shows the results of Comparative Example 1 , in which the ammonium ion concentration in wastewater was changed stepwise every 24 hours, and the conditions of ammonium ion concentration and nitrate ion concentration in treated water were shown.
【図５】 比較例２の結果であり、排水中のアンモニウ
ムイオン濃度を２４時間ごとに段階的に変化させ、処理
水中のアンモニウムイオン濃度、硝酸イオン濃度の状況
を示したものである。FIG. 5 shows the results of Comparative Example 2 in which the ammonium ion concentration in the wastewater was changed stepwise every 24 hours, and the conditions of the ammonium ion concentration and the nitrate ion concentration in the treated water were shown.
【図６】 実施例１の結果であり、排水中のアンモニウ
ムイオン濃度を２４時間ごとに段階的に変化させ、処理
水中のアンモニウムイオン濃度、硝酸イオン濃度の状況
を示したものである。FIG. 6 shows the results of Example 1 , in which the ammonium ion concentration in the wastewater is changed stepwise every 24 hours, and the situation of the ammonium ion concentration and the nitrate ion concentration in the treated water is shown.
フロントページの続き (72)発明者 三井 紀一郎 兵庫県姫路市網干区興浜字西沖992番地 の１ 株式会社日本触媒 触媒研究所内 審査官 真々田 忠博 (56)参考文献 特開 昭55−86584（ＪＰ，Ａ) 特開 平２−265696（ＪＰ，Ａ) 特開 平３−181390（ＪＰ，Ａ) 特開 昭59−55390（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C02F 1/74 C02F 1/58 B01J 3/00,9/00 Continuing from the front page (72) Inventor Kiichiro Mitsui 992, Nishioki, Okihama-shi, Himeji-shi, Himeji-shi JP-A-2-265696 (JP, A) JP-A-3-181390 (JP, A) JP-A-59-55390 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C02F 1 / 74 C02F 1/58 B01J 3 / 00,9 / 00
Claims (1)
化処理するに際し、あらかじめ処理水中のアンモニウム
イオン濃度および硝酸イオン濃度の最大許容濃度をそれ
ぞれＣ１およびＣ２と設定し、触媒湿式酸化装置より排
出される気液混合流体を気液分離した後、気相中の酸素
濃度、処理水中のアンモニウムイオン濃度および硝酸イ
オン濃度を測定し、測定された酸素濃度があらかじめ設
定された範囲内または濃度値、アンモニウムイオン濃度
値および硝酸イオン濃度値がそれぞれＣ１以下およびＣ
２以下となるように、装置内に流入させる酸素含有ガス
量を制御することを特徴とする触媒湿式酸化装置の制御
方法。When the wastewater containing ammonia nitrogen is subjected to catalytic wet oxidation treatment, the maximum allowable concentrations of ammonium ion and nitrate ion in the treated water are set to C1 and C2, respectively, and are discharged from the catalytic wet oxidation device. After gas-liquid separation of the gas-liquid mixed fluid, the oxygen concentration in the gas phase, the ammonium ion concentration and the nitrate ion concentration in the treated water are measured, and the measured oxygen concentration is within a preset range or a concentration value, The concentration value and the nitrate ion concentration value are C1 or less and C, respectively.
A method for controlling a catalytic wet oxidation apparatus, characterized by controlling the amount of oxygen-containing gas flowing into the apparatus so as to be 2 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05912794A JP3272859B2 (en) | 1994-03-29 | 1994-03-29 | Control method for catalytic wet oxidizer in treatment of wastewater containing ammonia nitrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05912794A JP3272859B2 (en) | 1994-03-29 | 1994-03-29 | Control method for catalytic wet oxidizer in treatment of wastewater containing ammonia nitrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07265881A JPH07265881A (en) | 1995-10-17 |
| JP3272859B2 true JP3272859B2 (en) | 2002-04-08 |
Family
ID=13104340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05912794A Expired - Fee Related JP3272859B2 (en) | 1994-03-29 | 1994-03-29 | Control method for catalytic wet oxidizer in treatment of wastewater containing ammonia nitrogen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3272859B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761041B (en) * | 2014-01-08 | 2017-02-22 | 万华化学集团股份有限公司 | Catalytic wet oxidation treatment reaction tower and method and device for treating high-concentration organic wastewater by using same |
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1994
- 1994-03-29 JP JP05912794A patent/JP3272859B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07265881A (en) | 1995-10-17 |
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