JPH0576879A - Treatment of waste water containing inorganic sulfur-containing compound - Google Patents
Treatment of waste water containing inorganic sulfur-containing compoundInfo
- Publication number
- JPH0576879A JPH0576879A JP24197491A JP24197491A JPH0576879A JP H0576879 A JPH0576879 A JP H0576879A JP 24197491 A JP24197491 A JP 24197491A JP 24197491 A JP24197491 A JP 24197491A JP H0576879 A JPH0576879 A JP H0576879A
- Authority
- JP
- Japan
- Prior art keywords
- waste water
- less
- pressure
- sulfur
- line
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 26
- 239000011593 sulfur Substances 0.000 title claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 16
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 6
- 229940006280 thiosulfate ion Drugs 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- -1 sulfur ions Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- KRURGYOKPVLRHQ-UHFFFAOYSA-L trithionate(2-) Chemical compound [O-]S(=O)(=O)SS([O-])(=O)=O KRURGYOKPVLRHQ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、硫黄の見かけの酸化数
が＋６未満の無機の硫黄を含む化合物を含有する廃水の
処理方法に関する。さらに詳しくは、本発明は、エチレ
ン製造プラント等の化学プラント等から排出される硫黄
の見かけの酸化数が＋６未満の無機の硫黄を含む化合物
を含有する廃水を、分子状酸素によって湿式酸化処理す
ることにより、廃水中に含有される該無機硫黄化合物を
無害な無機硫酸塩あるいは灰分等に転換せしめて廃水を
効率良く処理する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating wastewater containing an inorganic sulfur-containing compound having an apparent sulfur oxidation number of less than +6. More specifically, the present invention wet-oxidizes waste water containing a compound containing inorganic sulfur having an apparent sulfur oxidation number of less than +6 discharged from a chemical plant such as an ethylene production plant with molecular oxygen. Thus, the present invention relates to a method for efficiently treating wastewater by converting the inorganic sulfur compound contained in the wastewater into harmless inorganic sulfate or ash.
【０００２】[0002]
【従来の技術】従来、エチレン製造プラント等から排出
される硫化ソーダ等の硫化物で代表される、硫黄の見か
けの酸化数が＋６未満の無機の硫黄を含む化合物を含有
する廃水の処理は、該廃水中に塩化鉄を加えて硫化鉄と
して硫黄イオンを固定化した後、固液分離によって硫化
鉄を除去し、一方、分離液はｐＨ調製された後、活性汚
泥処理をして放流するという方法が一般的に行われてい
る。2. Description of the Related Art Conventionally, the treatment of waste water containing a compound containing inorganic sulfur having an apparent oxidation number of sulfur of less than +6, which is represented by sulfides such as sodium sulfide discharged from an ethylene production plant, is After iron chloride is added to the waste water to fix sulfur ions as iron sulfide, the iron sulfide is removed by solid-liquid separation, while the pH of the separated liquid is adjusted, and then activated sludge treatment is performed and discharged. The method is generally done.
【０００３】[0003]
【発明が解決しようとする課題】上記従来技術の方法で
は、硫化鉄を主成分とする汚泥が発生し、また処理プロ
セスとしても薬液注入、固液分離、ｐＨ調整、活性汚泥
処理と煩雑である。In the method of the prior art described above, sludge containing iron sulfide as a main component is generated, and the treatment process is complicated such as chemical liquid injection, solid-liquid separation, pH adjustment, and activated sludge treatment. ..
【０００４】従って、本発明の目的は、硫黄を含む化合
物を含有する廃水の処理に際して、簡便な処理プロセス
によって該廃水中に含有される硫黄成分を高度に無害化
しうる処理方法を提供することにある。Therefore, it is an object of the present invention to provide a treatment method capable of highly detoxifying a sulfur component contained in a waste water containing a compound containing sulfur by a simple treatment process. is there.
【０００５】[0005]
【課題を解決するための手段】上記目的は、本発明によ
れば、硫黄の見かけの酸化数が＋６未満の無機の硫黄を
含む化合物を含有する廃水を、３５０℃以下の温度かつ
該廃水が液相を保持する圧力下に、分子状酸素により湿
式酸化することを特徴とする無機の硫黄を含む化合物を
含有する廃水の処理方法によって達成される。According to the present invention, the above object is to provide a waste water containing a compound containing inorganic sulfur having an apparent oxidation number of sulfur of less than +6 at a temperature of 350 ° C. or lower at a temperature of 350 ° C. or lower. This is achieved by a method for treating wastewater containing an inorganic sulfur-containing compound, which is characterized in that it is wet-oxidized with molecular oxygen under a pressure that maintains a liquid phase.
【０００６】本発明によれば、硫黄の見かけの酸化数が
＋６未満の無機の硫黄を含む化合物を効率良く酸化分解
し、無機硫酸塩および灰分等に転換せしめることが可能
である。そして、必要に応じて、処理した廃水をｐＨ調
整して直接放流できる。このため、従来の設備と比較し
て非常に小さくなり、処理プロセスが簡素化され、設備
投資や、ランニングコストの面においても有利となる。According to the present invention, it is possible to efficiently oxidize and decompose an inorganic sulfur-containing compound having an apparent oxidation number of sulfur of less than +6 and convert it into an inorganic sulfate and ash. Then, if necessary, the treated wastewater can be pH-adjusted and directly discharged. For this reason, it is much smaller than the conventional equipment, the treatment process is simplified, and it is advantageous in terms of equipment investment and running cost.
【０００７】本発明における硫黄の見かけの酸化数が＋
６未満の無機の硫黄を含む化合物とは、硫化ソーダ、硫
化カリ等の硫化物類；チオ硫酸類およびその塩類；亜硫
酸類およびその塩類；三チオン酸、四チオン酸およびそ
の塩類等が挙げられる。In the present invention, the apparent oxidation number of sulfur is +
Examples of the compound containing inorganic sulfur of less than 6 include sulfides such as sodium sulfide and potassium sulfide; thiosulfates and salts thereof; sulfites and salts thereof; trithionate, tetrathionate and salts thereof, and the like. ..
【０００８】湿式酸化反応は、３５０℃以下の温度かつ
廃水が液相を保持する圧力下、前記の硫黄を含む化合物
が酸化分解されるのに必要な理論酸素量の１〜５倍量の
酸素ガスの存在下実施される。The wet oxidation reaction is carried out at a temperature of 350 ° C. or lower and at a pressure at which the wastewater retains a liquid phase, in an amount of 1 to 5 times the theoretical amount of oxygen required for oxidative decomposition of the sulfur-containing compound. It is carried out in the presence of gas.
【０００９】設備投資及びランニング等のコスト面よ
り、１８０℃未満の温度、かつ１０ｋｇ／ｃｍ2未満の
圧力下で湿式酸化反応が実施されることが好ましい。ま
た、この場合、空間速度（以下、ＬＨＳＶと記す）を
０．１〜１とすることが好ましい。ＬＨＳＶが、０．１
よりも小さい場合は処理時間が長くなり、処理装置が大
きなものとなって設備投資面で不利となり、またＬＨＳ
Ｖが１よりも大きい場合には充分な処理効率が得られな
い。From the viewpoint of costs such as equipment investment and running, it is preferable to carry out the wet oxidation reaction at a temperature of less than 180 ° C. and a pressure of less than 10 kg / cm 2 . In this case, the space velocity (hereinafter referred to as LHSV) is preferably 0.1-1. LHSV is 0.1
If it is smaller than this, the processing time becomes long, the processing equipment becomes large, and there is a disadvantage in terms of capital investment.
When V is larger than 1, sufficient processing efficiency cannot be obtained.
【００１０】本発明においては、硫黄化合物含有廃水の
処理後のｐＨは、中性からアルカリ性の範囲になるよう
に処理前あるいは処理中にアルカリ成分を供給しｐＨを
調整することが好ましい。酸性条件下における湿式酸化
処理では湿式酸化反応管材質の腐食が激しくなり、装置
の耐久性が著しく損なわれる恐れがある。In the present invention, the pH of the sulfur compound-containing wastewater after the treatment is preferably adjusted by supplying an alkaline component before or during the treatment so that the pH is in the neutral to alkaline range. In the wet oxidation treatment under acidic conditions, the material of the wet oxidation reaction tube is highly corroded, and the durability of the device may be significantly impaired.
【００１１】[0011]
【実施例】以下、本発明を実施例および比較例をあげて
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。The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these.
【００１２】（実施例１）図１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廃水を処理し
た。まずライン８より送られてくる廃水をポンプ３で
０.５リットル／Ｈｒの流量で９ｋｇ／ｃｍ2まで昇圧
し、一方、ライン９より供給される空気をコンプレッサ
ー５で昇圧した後、Ｏ2／ＴＯＤ（空気中の酸素量／理
論酸素要求量）＝１．２の割合で前記廃水に混入した。
この気液混合物をライン１０を経て、熱交換器２におい
て１５０℃に加熱した後、湿式酸化塔１へ導入した。湿
式酸化塔１において廃水を酸化処理し、被処理水をライ
ン１１を経て熱交換器２において冷却し、気液分離器４
へ流した。気液分離器４においては、液面コントローラ
（ＬＣ）により液面を検出して液面制御弁６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７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。Example 1 Waste water having the composition shown in Table 1 was treated according to the flow shown in FIG. First, the waste water sent from the line 8 is boosted to 9 kg / cm 2 by the pump 3 at a flow rate of 0.5 liter / hr, while the air supplied from the line 9 is boosted by the compressor 5 and then O 2 / The waste water was mixed in a ratio of TOD (oxygen amount in air / theoretical oxygen demand amount) = 1.2.
This gas-liquid mixture was heated to 150 ° C. in the heat exchanger 2 via the line 10 and then introduced into the wet oxidation tower 1. The waste water is oxidized in the wet oxidation tower 1, the water to be treated is cooled in the heat exchanger 2 via the line 11, and the gas-liquid separator 4 is used.
Shed to. In the gas-liquid separator 4, the liquid level controller (LC) detects the liquid level to operate the liquid level control valve 6 to maintain a constant liquid level, and the pressure controller (PC) detects the pressure. The pressure control valve 7 is operated to maintain a constant pressure.
【００１３】その結果、ＣＯＤＣｒ５２００ｍｇ／リッ
トル以下、硫化物イオン６００ｍｇ／リットル以下、チ
オ硫酸イオン３０００ｍｇ／リットル以下である被処理
水が安定して得られた。As a result, treated water having a CODCr of 5200 mg / liter or less, a sulfide ion of 600 mg / liter or less and a thiosulfate ion of 3000 mg / liter or less was stably obtained.
【００１４】表１ ＴＯＤ ２００００ｍｇ／リットル ｐＨ １３．８ Ｓ2~ １００００ｍｇ／リットル Ｎａ+ １６０００ｍｇ／リットル （実施例２）実施例１と同様のフローに従い、処理温度
を２００℃、処理圧力を４０ｋｇ／ｃｍ2として実験を
行った。このようにして処理を行った結果、処理水とし
てＣＯＤｃｒで３０００ｍｇ／リットル以下の処理水が
安定して得られた。また、処理水中の硫化物イオンは１
０ｍｇ／リットル以下であり、またチオ硫酸イオンにつ
いても２０００ｍｇ／リットル以下であった。Table 1 TOD 20000 mg / liter pH 13.8 S 2 to 10000 mg / liter Na + 16000 mg / liter (Example 2) According to the same flow as in Example 1, the treatment temperature was 200 ° C. and the treatment pressure was 40 kg / cm. The experiment was conducted as 2 . As a result of performing the treatment in this manner, treated water having a CODcr of 3000 mg / liter or less was stably obtained. In addition, the sulfide ion in the treated water is 1
It was 0 mg / liter or less, and thiosulfate ion was 2000 mg / liter or less.
【００１５】（実施例３）実施例１と同様のフローに従
い、処理温度を１２０℃、処理圧力を９ｋｇ／ｃｍ2と
して実験を行った。このようにして処理を行った結果、
処理水としてＣＯＤｃｒで７０００ｍｇ／リットル以下
の処理水が安定して得られた。また、処理水中の硫化物
イオンは８００ｍｇ／リットル以下であり、またチオ硫
酸イオンについても４０００ｍｇ／リットル以下であっ
た。(Example 3) According to the same flow as in Example 1, an experiment was conducted at a treatment temperature of 120 ° C and a treatment pressure of 9 kg / cm 2 . As a result of processing in this way,
As the treated water, treated water having a CODcr of 7,000 mg / liter or less was stably obtained. The sulfide ion content in the treated water was 800 mg / liter or less, and the thiosulfate ion content was 4000 mg / liter or less.
【００１６】（実施例４）実施例１と同様のフローに従
い、処理温度を１５０℃、処理圧力を９ｋｇ／ｃｍ2、
廃水流量０．２リットル／Ｈｒとして実験を行った。こ
のようにして処理を行った結果、処理水としてＣＯＤｃ
ｒで１２００ｍｇ／リットル以下の処理水が安定して得
られた。また、処理水中の硫化物イオンは０．１ｍｇ／
リットル以下であり、またチオ硫酸イオンについても１
０００ｍｇ／リットル以下であった。Example 4 According to the same flow as in Example 1, the processing temperature is 150 ° C., the processing pressure is 9 kg / cm 2 ,
The experiment was conducted with a wastewater flow rate of 0.2 liter / Hr. As a result of treatment in this way, CODc is treated as treated water.
With r, 1200 mg / liter or less of treated water was stably obtained. The sulfide ion in the treated water is 0.1 mg /
Less than 1 liter and 1 for thiosulfate ion
It was 000 mg / liter or less.
【００１７】（実施例５）実施例１と同様のフローに従
い、処理温度を１５０℃、処理圧力を９ｋｇ／ｃｍ2、
廃水流量２リットル／Ｈｒとして実験を行った。このよ
うにして処理を行った結果、処理水としてＣＯＤｃｒで
１２０００ｍｇ／リットル以下の処理水が安定して得ら
れた。また、処理水中の硫化物イオンは４０００ｍｇ／
リットル以下であり、またチオ硫酸イオンについても３
０００ｍｇ／リットル以下であった。(Embodiment 5) According to the same flow as in Embodiment 1, the treatment temperature is 150 ° C., the treatment pressure is 9 kg / cm 2 ,
The experiment was conducted with a waste water flow rate of 2 liters / Hr. As a result of performing the treatment in this manner, treated water having a CODcr of 12,000 mg / liter or less was stably obtained. In addition, the sulfide ion in the treated water is 4000 mg /
Less than 1 liter, and also for thiosulfate ion 3
It was 000 mg / liter or less.
【００１８】[0018]
【発明の効果】本発明によれば、簡便な操作によって、
廃水中に含有されている硫黄の見かけの酸化数が＋６未
満の無機の硫黄を含む化合物を効率良く酸化分解し、無
機硫酸塩および灰分等に転換せしめることが可能であ
る。According to the present invention, by a simple operation,
It is possible to efficiently oxidatively decompose an inorganic sulfur-containing compound having an apparent oxidation number of less than +6 contained in the wastewater and convert it into an inorganic sulfate and ash.
【図１】本発明方法を実施する際の一態様を示すフロー
チャート図である。FIG. 1 is a flow chart diagram showing one mode for carrying out the method of the present invention.
１．湿式反応塔 ２．熱交換器 ３．廃水供給ポンプ ４．気液分離器 ５．コンプレッサー ６．液面制御弁 ７．圧力制御弁 1. Wet reaction tower 2. Heat exchanger 3. Waste water supply pump 4. Gas-liquid separator 5. Compressor 6. Liquid level control valve 7. Pressure control valve
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 (72)発明者 佐野 邦夫 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Front page continuation (72) Inventor Kiichiro Mitsui 1 992 Nishikioki, Akihama, Himeji-shi, Hyogo Prefecture, Japan Catalysis Research Institute Co., Ltd. Catalyst Catalyst Research Center
Claims (2)
の硫黄を含む化合物を含有する廃水を、３５０℃以下の
温度かつ該廃水が液相を保持する圧力下に、分子状酸素
により湿式酸化することを特徴とする硫黄を含む化合物
を含有する廃水の処理方法。1. A wet water containing a compound containing an inorganic sulfur having an apparent oxidation number of sulfur of less than +6 is wetted with molecular oxygen at a temperature of 350 ° C. or lower and at a pressure at which the waste water holds a liquid phase. A method for treating wastewater containing a sulfur-containing compound characterized by being oxidized.
ｋｇ／ｃｍ2未満の圧力下に湿式酸化する請求項１記載
の無機の硫黄を含む化合物を含有する廃水の処理方法。2. The wastewater at a temperature of less than 180 ° C. and 10
The method for treating wastewater containing an inorganic sulfur-containing compound according to claim 1, wherein the wet oxidation is carried out under a pressure of less than kg / cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24197491A JPH0576879A (en) | 1991-09-20 | 1991-09-20 | Treatment of waste water containing inorganic sulfur-containing compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24197491A JPH0576879A (en) | 1991-09-20 | 1991-09-20 | Treatment of waste water containing inorganic sulfur-containing compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0576879A true JPH0576879A (en) | 1993-03-30 |
Family
ID=17082362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24197491A Pending JPH0576879A (en) | 1991-09-20 | 1991-09-20 | Treatment of waste water containing inorganic sulfur-containing compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0576879A (en) |
-
1991
- 1991-09-20 JP JP24197491A patent/JPH0576879A/en active Pending
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