JPH0368494A - Treatment of waste water containing dimethyl disulfide - Google Patents
Treatment of waste water containing dimethyl disulfideInfo
- Publication number
- JPH0368494A JPH0368494A JP20488489A JP20488489A JPH0368494A JP H0368494 A JPH0368494 A JP H0368494A JP 20488489 A JP20488489 A JP 20488489A JP 20488489 A JP20488489 A JP 20488489A JP H0368494 A JPH0368494 A JP H0368494A
- Authority
- JP
- Japan
- Prior art keywords
- dimethyl disulfide
- hydrogen
- reduced iron
- contact
- dmds
- 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
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002351 wastewater Substances 0.000 title claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 15
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 30
- 239000001257 hydrogen Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000843 powder Substances 0.000 abstract description 12
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241001522296 Erithacus rubecula Species 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、廃水の処理法に関し、特にクラフトパルプＷ
Ｊ造工場、魚腸骨、厘尿下水処ＦＪ場から排出される廃
水等、二硫化ジメチル含有廃水を処理する方法に間する
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for treating wastewater, and in particular to a method for treating wastewater using kraft pulp W.
We will develop a method for treating wastewater containing dimethyl disulfide, such as wastewater discharged from the FJ plant, fish iliac plant, and sewage treatment plant.
（従来の技術及び発明が解決しようとする課題〉従来、
二硫化ジメチル（Ｄｉｍｅｔｈｙｌ Ｄｉｓｕｌｆｉｄ
ｅ；ＤＭＤＳ）が多量に含まれている廃水を処理する場
合は、一般にガスストリッピング法などによって分離さ
れていた。(Problems to be solved by conventional techniques and inventions) Conventionally,
Dimethyl Disulfide
When treating wastewater that contains a large amount of DMDS, it is generally separated by a gas stripping method or the like.
しかし、ガスストリッピングによる分離方法では非常に
大きな動力を必要とすること、また、分離されたものは
通常、ひどい悪臭を伴うので、後処理が非常に困難であ
る問題があった。However, the separation method by gas stripping requires a very large amount of power, and the separated product usually has a strong odor, making post-treatment very difficult.
なお、ガスストリッピング処理をしない廃液では、活性
汚泥等の生物処理を行うにしても負荷の増大を招き、経
済的な問題があった。In addition, waste liquid that is not subjected to gas stripping treatment causes an increase in load even if biological treatment such as activated sludge is performed, which poses an economic problem.
（課題を解決するための手段）
本発明者らは上記課題に鑑み、廃水中の二硫化ジメチル
の除去について鋭意研究した結果、二硫化ジメチルは化
学構造がそれほど安定ではないので、水素との接触面を
与えさえすれば容易に分解するであろうと推測し、実験
を重ねて、本発明をなすに至った。(Means for Solving the Problems) In view of the above problems, the present inventors have conducted extensive research on the removal of dimethyl disulfide from wastewater, and have found that dimethyl disulfide has a not very stable chemical structure, so it cannot be removed by contact with hydrogen. We surmised that it would be easily decomposed as long as we gave it a surface, and after repeated experiments we came up with the present invention.
本発明はすなわち、二硫化ジメチル含有廃水を、水素ガ
ス単独に接触させるか、あるいは触媒又は還元金属と共
に、水素ガスに接触させることにより、二硫化ジメチル
を還元分解して気化除去することを特徴とする二硫化ジ
メチル含有廃水の処理法である。That is, the present invention is characterized in that dimethyl disulfide is reductively decomposed and vaporized and removed by bringing dimethyl disulfide-containing wastewater into contact with hydrogen gas alone or with hydrogen gas together with a catalyst or reducing metal. This is a method for treating wastewater containing dimethyl disulfide.
上記本発明方法によれば、廃水から二硫化ジメチルを容
易に除去することができる。According to the method of the present invention described above, dimethyl disulfide can be easily removed from wastewater.
本発明において、廃液と水素との接触方法は、廃水中に
水素気泡を直接導入して気液接触させてもよいが、還元
鉄、還元銅等の還元金属触媒と共に水素を接触させるこ
とが好ましい。In the present invention, the method of contacting the waste liquid with hydrogen may be to directly introduce hydrogen bubbles into the waste water to cause gas-liquid contact, but it is preferable to contact the hydrogen with a reducing metal catalyst such as reduced iron or reduced copper. .
触媒としては、特に安価で水素貯蔵性に優れる還元鉄が
好ましいが、このほかに、例えば還元銅、ラネーＮｉ、
白金、パラジウムなどの接触水素化触媒等が挙げられる
。As a catalyst, reduced iron is particularly preferable because it is inexpensive and has excellent hydrogen storage properties, but in addition, reduced copper, Raney Ni,
Examples include catalytic hydrogenation catalysts such as platinum and palladium.
これらは、二硫化ジメチルに水素を付加して還元させる
効果をもつ触媒である。These are catalysts that have the effect of adding hydrogen to dimethyl disulfide and reducing it.
ところで、二硫化ジメチルやメチルメルカプタンは含硫
黄有機化合物であって、触媒毒となる場合がある。これ
を回避するため、これら触媒毒に対して対抗性の強い触
媒として、パラジウムブラック等を用いることができる
が、これらはコストが非常に高いものとなる。By the way, dimethyl disulfide and methyl mercaptan are sulfur-containing organic compounds and may act as catalyst poisons. In order to avoid this, palladium black or the like can be used as a catalyst that is highly resistant to these catalyst poisons, but these are extremely expensive.
しかし、触媒毒となる場合であっても、充分に再生処理
を行うことによって、それを連続使用して経済性を高め
るようにしてもよい。However, even if it becomes a catalyst poison, it may be used continuously to improve economic efficiency by performing sufficient regeneration treatment.
（作用）
二硫化ジメチル（Ｃ２ＨＩ Ｓ２）は、沸点が１１０℃
、比重約１．０６であるため、水中に存在しやすい。(Function) Dimethyl disulfide (C2HI S2) has a boiling point of 110°C
, has a specific gravity of about 1.06, so it easily exists in water.
しかし、還元されると次式（１）により、ＣＨｓ −Ｓ
−Ｓ −ＣＨｓ ＋ Ｈｔ →２ＣＨ，ＳＨ（１）
に示すとおり、メチルメルカプタン（ＣＨ（Ｓ ）に還
元、分解される。However, when reduced, CHs -S
-S -CHs + Ht →2CH, SH (1)
As shown, it is reduced and decomposed to methyl mercaptan (CH(S)).
すると、メチルメルカプタンの沸点は５．９５℃で低く
いものであるため、容易に空気中に移行することとなり
、その分離、除去が達成される。Then, since methyl mercaptan has a low boiling point of 5.95°C, it easily migrates into the air, and its separation and removal can be achieved.
〈実施例） 次に、本発明の実施例を図面に基づいて、説明する。<Example) Next, embodiments of the present invention will be described based on the drawings.
実施例１：
第１１２Ｉは本発明実施例方法のフローシートであり、
処理される廃水〈原料水〉は、まずポンプＰで接触還元
塔１に送給される。Example 1: No. 112I is a flow sheet of the method of the present invention,
Wastewater to be treated (raw water) is first fed to the catalytic reduction tower 1 by a pump P.
接触還元塔１は、たて型の塔状体であり、内部には還元
鉄の粉末が充填され、ｍ張体を形成している。The catalytic reduction tower 1 is a vertical tower-like body, and the inside thereof is filled with reduced iron powder to form an m-tensioned body.
該接触還元塔１には原料水中に含有されるＤＭＤＳ（二
硫化ジメチル）と還元鉄の接触効率を上げるため、水素
ガスの供給、循環が行われ、接触廃水中における還元鉄
粉末の占める体積割合を増加させるようにしている。In order to increase the contact efficiency between DMDS (dimethyl disulfide) and reduced iron contained in the raw water, hydrogen gas is supplied and circulated to the catalytic reduction tower 1, and the volume ratio of reduced iron powder in the contact wastewater is reduced. We are trying to increase this.
循環水素ガスの量は、還元鉄がかなりの体積の貯蔵水素
を含んでいることから、少量でよく、せいぜい細かな還
元鉄の粉末が槽内に広がるのに必要な量でよい、処理の
終わった水は還元鉄とともに気固液分離器２に送られる
。Since reduced iron contains a considerable volume of stored hydrogen, the amount of circulating hydrogen gas may be small, at most the amount necessary to spread fine reduced iron powder in the tank. The water is sent to the gas-solid-liquid separator 2 together with reduced iron.
還元鉄は沈降性がよいので、その分離器２は小さいもの
で済み、それから分離された水は処理水となる。なお、
分離された還元鉄（Ｓｏｌｉｄ Ｆｅ）は再活性化させ
て、接触塔１へ供給することが望ましい。Since reduced iron has good sedimentation properties, the separator 2 can be small, and the water separated therefrom becomes treated water. In addition,
It is desirable that the separated reduced iron (Solid Fe) be reactivated and supplied to the contact column 1.
上記実施例においては、接触還元塔における充填剤とし
て還元鉄粉末を使用したが、必要に応じその他の還元金
属粉末を使用してもよい。In the above embodiments, reduced iron powder was used as the filler in the catalytic reduction tower, but other reduced metal powders may be used as necessary.
さらに、充填剤を使用することなく、水素のみを使用し
て実施してもよい。Furthermore, it may be carried out using only hydrogen without using a filler.
実施例２： 第２図は他の実施例方法のフローシートであり。Example 2: FIG. 2 is a flow sheet of another example method.
まず、処理される廃水（原水）が接触還元塔１に送給さ
れる。First, wastewater (raw water) to be treated is sent to the catalytic reduction tower 1.
接触還元塔１の内部には還元鉄の粉末が流動状態で充填
されている。The inside of the catalytic reduction tower 1 is filled with reduced iron powder in a fluidized state.
第１実施例の場合と同様に、該接触還元塔には原水中に
含有されるＤＭＤＳ（二硫化ジメチル）と還元鉄の接触
効率を上げるため、水素ガスの供給、循環が行われ、接
触廃水中における還元鉄粉末の占める体積割合を増加さ
せるようにしている。As in the case of the first embodiment, hydrogen gas is supplied and circulated to the catalytic reduction tower in order to increase the contact efficiency between DMDS (dimethyl disulfide) contained in the raw water and reduced iron, and the catalytic reduction tower The volume ratio occupied by the reduced iron powder inside is increased.
処理の終わった水は還元鉄とともに気固液分離器２に送
られる。The treated water is sent to the gas-solid-liquid separator 2 together with reduced iron.
気固液分離器２からは、液体としての処理水と、気体と
しての水素とメチルメルカプタンのガスと、固体として
の還元鉄（Ｆｅ）が導出される。From the gas-solid-liquid separator 2, treated water as a liquid, hydrogen and methyl mercaptan gas as gases, and reduced iron (Fe) as a solid are led out.
排出された還元鉄は、脱水された後、還元鉄再生装置３
に導入され、再活性化される。The discharged reduced iron is dehydrated and then sent to the reduced iron regeneration device 3.
introduced and reactivated.
還元鉄再生装置３は、その一端から水素が導入され、他
端から再生された還元鉄と水素の混合体が導出される。Hydrogen is introduced into the reduced iron regeneration device 3 from one end thereof, and a mixture of regenerated reduced iron and hydrogen is led out from the other end.
導出された還元鉄と水素の混合体は、再び接触還元塔１
へ導入される。The derived mixture of reduced iron and hydrogen is sent to the catalytic reduction tower 1 again.
will be introduced to
ところで、使用済還元鉄を再活性化するためには若干の
熱量を必要とするが、本実施例方法においては、気固液
分離器２から排出された二硫化ジメチルの分解生成物で
ある水素とメチルメルカプタンとのガス混合体を還元鉄
再生装置３の加熱用燃料として利用する。By the way, a certain amount of heat is required to reactivate spent reduced iron, but in the method of this embodiment, hydrogen, which is a decomposition product of dimethyl disulfide discharged from the gas-solid-liquid separator 2, is A gas mixture of methyl mercaptan and methyl mercaptan is used as a heating fuel for the reduced iron regeneration device 3.
さらに、該装置３においては再活性化に水素ガスが用い
られ、排出される余剰水素は再活性化された還元鉄とと
もに接触還元塔１に送られる。Further, in the device 3, hydrogen gas is used for reactivation, and the excess hydrogen discharged is sent to the catalytic reduction tower 1 together with the reactivated reduced iron.
本実施例方法によれば、エネルギーコストが低減され、
クローズドシステム化もできるため、非常に有利である
。According to the method of this embodiment, energy costs are reduced;
It is very advantageous because it can be made into a closed system.
実施例３：
次に、本発明方法の効果をビーカースケールで試験した
結果を説明する。Example 3: Next, the results of testing the effectiveness of the method of the present invention on a beaker scale will be explained.
容量１５０ｍ１のねじロビン（ゴム栓１寸き）に二硫「
ヒソメチル２０００ｐｐ
を入れ，このビンのヘッドスペースガス（上部ガス）を
水素ガスで置換した後、びん口にゴム栓をして密封した
。Disulfurized into a screw robin (1 inch rubber stopper) with a capacity of 150 m1
After adding 2000 pp of hisomethyl and replacing the head space gas (upper gas) of this bottle with hydrogen gas, the bottle mouth was sealed with a rubber stopper.
該密封ねじロビンを振どう後、５分間放置して水素と含
有二硫化ジメチルを反応させた後、液中の二硫化ジメチ
ル濃度をガスクロマトグラフィで測定した。After shaking the sealed screw robin, it was left to stand for 5 minutes to allow hydrogen to react with the dimethyl disulfide contained therein, and then the concentration of dimethyl disulfide in the liquid was measured by gas chromatography.
その結果，液中濃度は１，５００ｐｐｍであって、二硫
化ジメチルの除去率は２５％であった。As a result, the concentration in the liquid was 1,500 ppm, and the removal rate of dimethyl disulfide was 25%.
実施例４：
実施例３は水素ガス単独で接触除去した例であるが、本
例では還元金属粉と併用して接触せしめた． 使用還元
金属粉の種類とその成端は第１表に示すとおりであった
。Example 4: Example 3 was an example in which hydrogen gas was used alone for contact removal, but in this example, it was used in combination with reduced metal powder. The type of reduced metal powder used and its termination are as shown in Table 1.
なお、ねじロビン、二硫化ジメチル含有水の濃度及び使
用量は、実施例３と同じであり、各還元金属粉は０．１
ｇづつ使用した。The concentration and amount of water containing Nejirobin and dimethyl disulfide are the same as in Example 3, and each reduced metal powder has a concentration of 0.1
g each was used.
素ガスを単独であるいは還元金属と共に接触させて還元
するだけで、容易に二硫化ジメチルを分解除去すること
ができる．したがって、従来法のような大規模装置を必
要としない。Dimethyl disulfide can be easily decomposed and removed simply by reducing it by bringing it into contact with an elementary gas alone or together with a reducing metal. Therefore, large-scale equipment unlike the conventional method is not required.
また、分解生成物ガスを本発明方法の還元金属再生装置
に使用すれば、エネルギーコストが低減され、クローズ
ドシステム化もできる。Moreover, if the decomposition product gas is used in the reduced metal regeneration apparatus of the method of the present invention, energy costs can be reduced and a closed system can be achieved.
第１図は本発明実施例のフローシート図、第２図は他の
実施例のフローシート図である。FIG. 1 is a flow sheet diagram of an embodiment of the present invention, and FIG. 2 is a flow sheet diagram of another embodiment.
Claims (3)
ることにより、二硫化ジメチルを還元分解して気化除去
することを特徴とする二硫化ジメチル含有廃水の処理法
。(1) A method for treating wastewater containing dimethyl disulfide, which comprises bringing the wastewater containing dimethyl disulfide into contact with hydrogen gas to reductively decompose and vaporize and remove dimethyl disulfide.
接触させ、かつ同時に水素ガスに接触させることにより
、二硫化ジメチルを還元分解して気化除去することを特
徴とする二硫化ジメチル含有廃水の処理法。(2) A wastewater containing dimethyl disulfide characterized by bringing the wastewater containing dimethyl disulfide into contact with a catalyst or a reducing metal and at the same time contacting with hydrogen gas to reductively decompose and vaporize and remove dimethyl disulfide. Processing method.
プタンを触媒又は還元金属の再生用燃料に使用すること
を特徴とする請求項２記載の二硫化ジメチル含有廃水の
処理法。(3) The method for treating dimethyl disulfide-containing wastewater according to claim 2, characterized in that methyl mercaptan produced by decomposing dimethyl disulfide is used as a catalyst or a fuel for regenerating reduced metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20488489A JPH0368494A (en) | 1989-08-09 | 1989-08-09 | Treatment of waste water containing dimethyl disulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20488489A JPH0368494A (en) | 1989-08-09 | 1989-08-09 | Treatment of waste water containing dimethyl disulfide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0368494A true JPH0368494A (en) | 1991-03-25 |
Family
ID=16497993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20488489A Pending JPH0368494A (en) | 1989-08-09 | 1989-08-09 | Treatment of waste water containing dimethyl disulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0368494A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591368A (en) * | 2015-01-26 | 2015-05-06 | 大连理工大学 | Iron-coal ash-kaolin filler and method for reductively converting nitro-aromatic waste water |
-
1989
- 1989-08-09 JP JP20488489A patent/JPH0368494A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591368A (en) * | 2015-01-26 | 2015-05-06 | 大连理工大学 | Iron-coal ash-kaolin filler and method for reductively converting nitro-aromatic waste water |
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