JPS6327284B2 - - Google Patents
Info
- Publication number
- JPS6327284B2 JPS6327284B2 JP6198783A JP6198783A JPS6327284B2 JP S6327284 B2 JPS6327284 B2 JP S6327284B2 JP 6198783 A JP6198783 A JP 6198783A JP 6198783 A JP6198783 A JP 6198783A JP S6327284 B2 JPS6327284 B2 JP S6327284B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrazine
- ethylene oxide
- water
- systems
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 24
- -1 Fatty acid ethylene oxide Chemical class 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 150000003871 sulfonates Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 16
- 150000002429 hydrazines Chemical class 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000012806 monitoring device Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229940123973 Oxygen scavenger Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 239000006481 glucose medium Substances 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Description
この発明はヒドラジン化合物の安定化剤に関す
るものである。
ヒドラジン化合物は還元性を有し、用廃水系に
おける水処理剤として使用されている。水処理剤
としては、ボイラ等の密閉系における脱酸素剤、
冷却水系、製紙用水系等の開放系におけるスライ
ム防除剤として、防食剤、スケール防止剤等の他
の薬剤とともに使用されている。
ところが、ヒドラジン化合物は不安定で、水中
の溶存酸素によつて分解されるほか、PH4以上で
金属イオンが存在する系や金属材料が使われてい
る系では、溶存酸素に見合う量以上のヒドラジン
化合物が激しく分解する。このためスライム防止
効果等の水処理効果を維持するためには、多量の
ヒドラジン化合物を使用する必要があり、処理コ
ストを高くするとともに、高濃度のヒドラジン化
合物は銅材料を腐食するなどの問題があつた。
この発明は、このような問題点を解決するため
のもので、ヒドラジン化合物の分解を防止し、水
処理効果を維持できる安定化剤を提供することを
目的としている。
脂肪酸エチレンオキシド付加物、アルキルフエ
ノールエチレンオキシド付加物、ソルビタン脂肪
酸エステル、ポリプロピレングリコールエチレン
オキシド付加物、ポリオキシエチレンアルキルア
ミン、第四アンモニウム塩、第四ホスホニウム
塩、アミノ酸塩、およびジアルキルエステルスル
ホン酸塩から選ばれる1種以上の界面活性剤を有
効成分とすることを特徴とするヒドラジンおよび
ヒドラジン水加物から選ばれるヒドラジン化合物
の安定化剤。
本発明において安定化の対象となるヒドラジン
化合物は、ヒドラジノ基を有する化合物であつ
て、ヒドラジン、およびヒドラジン水加物から選
ばれるものである。
界面活性剤としては、脂肪酸エチレンオキシド
付加物、アルキルフエノールエチレンオキシド付
加物、ソルビタン脂肪酸エステル、ポリプロピレ
ングリコールエチレンオキシド付加物、ポリオキ
シエチレンアルキルアミン、第四アンモニウム
塩、第四ホスホニウム塩、アミノ酸塩、およびジ
アルキルエステルスルホン酸塩から選ばれる1種
以上のものがある。
これらの界面活性剤はヒドラジン化合物の分解
が問題となる系に添加して使用される。ヒドラジ
ン化合物の分解が問題となる系としては、水処理
剤などの薬剤として使用前の製品に分解が起こる
系、ならびに薬剤の使用中に分解が起こる系など
が挙げられる。
使用前に分解が起こる系では、薬剤中に界面活
性剤を添加する。また使用中に分解が起こる系で
は、界面活性剤を薬剤中に配合してもよく薬品と
ともにまた別々に対象系へ直接添加してもよい。
安定化の対象となるヒドラジン化合物は、単独
で対象系へ添加される場合でもよく、他の薬剤と
ともに対象系へ添加される場合でもよい。ヒドラ
ジン化合物は水処理剤として使用する場合、密閉
系においては主に脱酸素剤やスライム防除剤等と
して使用され、開放系においては主にスライム防
除剤として使用されており、いずれの場合も単独
で使用する場合および他の薬剤との組合せで使用
する場合がある。組合せで使用する薬剤としては
防食剤、スケール防止剤などが挙げられる。
界面活性剤の添加量は、薬剤製品中における分
解を防止する場合は、ヒドラジン類に対して0.01
〜50重量%、対象系における分解を防止する場合
は、界面活性剤の濃度として0.1〜100mg/程度
である。
上記説明は、ヒドラジン化合物を水処理薬剤と
して使用する場合についてのものであるが、他の
用途においても同様に安定化を行うことができ
る。
以上説明してきたように、この発明によれば、
不安定なヒドラジン化合物を安定化して、その分
解を防止し、水処理活性等の活性を高く維持する
ことができ、このためヒドラジン化合物の使用量
を少なくするとともに、添加濃度を低くして銅材
等に対する腐食性を低くすることができる。また
ヒドラジン化合物を水処理薬剤として使用する場
合、スライム防除効果を極めて良好にするほか、
スケール防止効果および防食効果も改善される。
次に本発明の実施例について説明する。
実施例 1
PH8.5、カルシウム硬度300mg/asCaCO3、M
アルカリ度300mg/asCaCO3の水に銅テストピ
ース(30mm×50mm)1枚を浸漬し、30℃、
300rpmでスターラ撹拌した系に、ヒドラジン20
mg/および各種界面活性剤を表1に示す添加量
で添加し、ブランクがOとなつた48時間後のヒド
ラジンの残留率を次式により求めた。
結果を表1に併記する。
残留率=48時間後のN2H4濃度(mg/)/初期N2H4濃度
(mg/)×100
表1中、No.9はツイン80(花王石鹸KK)、No.11
はエソミンT25(ライオンKK)、No.12はα−アル
コキシプロピルジメチルベンジルアンモニウムク
ロライド、No.13はベルクレン350(チバガイギー
社)、No.14はオパノール516(東邦化学KK)、No.15
はエアロゾルOT(三洋化成工業KK)である。
This invention relates to a stabilizer for hydrazine compounds. Hydrazine compounds have reducing properties and are used as water treatment agents in industrial and wastewater systems. Water treatment agents include oxygen scavengers for closed systems such as boilers,
It is used as a slime control agent in open systems such as cooling water systems and papermaking water systems, together with other agents such as anticorrosive agents and scale inhibitors. However, hydrazine compounds are unstable and are decomposed by dissolved oxygen in water, and in systems where metal ions are present or metal materials are used at a pH of 4 or higher, hydrazine compounds may be decomposed in amounts greater than the amount of dissolved oxygen. decomposes violently. Therefore, in order to maintain water treatment effects such as slime prevention effects, it is necessary to use large amounts of hydrazine compounds, which increases treatment costs and causes problems such as high concentrations of hydrazine compounds corroding copper materials. It was hot. This invention is intended to solve these problems, and aims to provide a stabilizer that can prevent the decomposition of hydrazine compounds and maintain water treatment effects. 1 selected from fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, sorbitan fatty acid esters, polypropylene glycol ethylene oxide adducts, polyoxyethylene alkylamines, quaternary ammonium salts, quaternary phosphonium salts, amino acid salts, and dialkyl ester sulfonates A stabilizer for a hydrazine compound selected from hydrazine and hydrazine hydrate, characterized by containing at least one surfactant as an active ingredient. The hydrazine compound to be stabilized in the present invention is a compound having a hydrazino group, and is selected from hydrazine and hydrazine hydrate. Surfactants include fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, sorbitan fatty acid esters, polypropylene glycol ethylene oxide adducts, polyoxyethylene alkylamines, quaternary ammonium salts, quaternary phosphonium salts, amino acid salts, and dialkyl ester sulfones. There is one or more types selected from acid salts. These surfactants are used by adding them to systems where decomposition of hydrazine compounds is a problem. Examples of systems in which decomposition of hydrazine compounds is a problem include systems in which decomposition occurs in a product before use as a chemical such as a water treatment agent, and systems in which decomposition occurs during use of the chemical. In systems where degradation occurs prior to use, surfactants are added to the drug. Furthermore, in systems where decomposition occurs during use, a surfactant may be incorporated into the drug or added directly to the target system together with the drug or separately. The hydrazine compound to be stabilized may be added to the target system alone or together with other drugs. When hydrazine compounds are used as water treatment agents, they are mainly used as oxygen scavengers and slime control agents in closed systems, and as slime control agents in open systems. May be used and in combination with other drugs. Examples of agents used in combination include anticorrosive agents and anti-scaling agents. When preventing decomposition in drug products, the amount of surfactant added should be 0.01 to hydrazines.
~50% by weight, and when preventing decomposition in the target system, the concentration of the surfactant is approximately 0.1 to 100 mg/. Although the above description concerns the use of the hydrazine compound as a water treatment agent, stabilization can be performed in other applications as well. As explained above, according to this invention,
It is possible to stabilize unstable hydrazine compounds, prevent their decomposition, and maintain high activities such as water treatment activity. Therefore, the amount of hydrazine compounds used can be reduced, and the concentration of additives can be lowered to improve copper materials. It is possible to reduce the corrosiveness against etc. In addition, when hydrazine compounds are used as water treatment agents, they have extremely good slime control effects, and
The anti-scaling and anti-corrosion effects are also improved. Next, examples of the present invention will be described. Example 1 PH8.5, calcium hardness 300mg/asCaCO 3 , M
One copper test piece (30mm x 50mm) was immersed in water with an alkalinity of 300mg/asCaCO 3 , and heated at 30℃.
Add hydrazine 20 to a system stirred at 300 rpm.
mg/ml and various surfactants were added in the amounts shown in Table 1, and the residual rate of hydrazine 48 hours after the blank became O was determined by the following formula. The results are also listed in Table 1. Residual rate = N 2 H 4 concentration after 48 hours (mg/) / Initial N 2 H 4 concentration (mg/) × 100 In Table 1, No. 9 is Twin 80 (Kao Soap KK), No. 11
is Esomin T25 (Lion KK), No. 12 is α-alkoxypropyldimethylbenzyl ammonium chloride, No. 13 is Verklein 350 (Ciba Geigy), No. 14 is Opanol 516 (Toho Chemical KK), No. 15
is Aerosol OT (Sanyo Chemical Industries KK).
【表】【table】
【表】
実施例 2
表2の水処理薬剤について、開放循環水系のモ
ニター装置により試験を行つた。[Table] Example 2 The water treatment chemicals shown in Table 2 were tested using an open circulating water system monitoring device.
【表】
モニター装置は、保有水量15、循環水量300
/hr、流速0.5m/s、滞留時間120hr、伝熱チ
ユーブ(SUS製、伝熱面積0.0471m2)の入口温度
30℃、出口温度35℃、平均表面温度50℃であり、
スライム付着用に非伝熱チユーブ(SUS単管、
伝熱面積0.0471m2)を使用し、常時30℃の温水を
300/hr、流速5m/sで通水し、循環ピツト
中に軟鋼および銅テストピースを浸漬した。
試験水は、カルシウム硬度500mg/、Mアル
カリ度500mg/の合成水であり、スライム発生
促進のため活性汚泥を乾燥重量として2g添加
し、ペプトングルコース培地をBOD負荷として
10g/m3・day投入した。
試験は表2の薬剤をそれぞれモニター装置の循
環水に、初期には対保有水量あたり200mg/と
なるように投入し、以後はブロー水あたり200
mg/になるように投入して、約2週間通水し、
スライム付着量、スケール付着量、銅および軟鋼
テストピース腐食速度、ならびにヒドラジン残留
濃度を測定した。結果を表3に示す。なおスケー
ル付着量は伝熱チユーブの全付着物量から強熱減
量を差引いた値である。[Table] The monitoring device has a holding water volume of 15 and a circulating water volume of 300.
/hr, flow rate 0.5m/s, residence time 120hr, inlet temperature of heat transfer tube (made of SUS, heat transfer area 0.0471m 2 )
30℃, outlet temperature 35℃, average surface temperature 50℃,
Non-heat transfer tube (SUS single tube,
A heat transfer area of 0.0471m2 ) is used to constantly supply hot water at 30℃.
Mild steel and copper test pieces were immersed in the circulation pit by passing water at a rate of 300/hr and a flow rate of 5 m/s. The test water was synthetic water with a calcium hardness of 500 mg/m and an alkalinity of 500 mg/m, to which 2 g of activated sludge was added as a dry weight to promote slime generation, and a peptone glucose medium was added as a BOD load.
10g/m 3・day was added. In the test, each of the chemicals listed in Table 2 was added to the circulating water of the monitoring device at an initial concentration of 200 mg per amount of water held, and thereafter at a concentration of 200 mg per blown water.
mg/, and water was passed for about 2 weeks.
The amount of slime adhesion, the amount of scale adhesion, the corrosion rate of copper and mild steel test pieces, and the residual concentration of hydrazine were measured. The results are shown in Table 3. Note that the amount of scale adhesion is the value obtained by subtracting the loss on ignition from the total amount of adhesion on the heat transfer tube.
【表】
表3の結果より、本発明薬剤は対照薬剤に比べ
て、ヒドラジン残留濃度が高く、スライム防除効
果が極めて良好であり、スケール防止効果および
防食効果も良くなることがわかる。[Table] From the results in Table 3, it can be seen that the agent of the present invention has a higher residual hydrazine concentration, has an extremely good slime control effect, and has better scale prevention and corrosion prevention effects than the control agent.
Claims (1)
エノールエチレンオキシド付加物、ソルビタン脂
肪酸エステル、ポリプロピレングリコールエチレ
ンオキシド付加物、ポリオキシエチレンアルキル
アミン、第四アンモニウム塩、第四ホスホニウム
塩、アミノ酸塩、およびジアルキルエステルスル
ホン酸塩から選ばれる1種以上の界面活性剤を有
効成分とすることを特徴とするヒドラジンおよび
ヒドラジン水加物から選ばれるヒドラジン化合物
の安定化剤。 2 ヒドラジン化合物は水処理用のものである特
許請求の範囲第1項記載のヒドラジン化合物の安
定化剤。[Claims] 1 Fatty acid ethylene oxide adduct, alkylphenol ethylene oxide adduct, sorbitan fatty acid ester, polypropylene glycol ethylene oxide adduct, polyoxyethylene alkylamine, quaternary ammonium salt, quaternary phosphonium salt, amino acid salt, and dialkyl ester A stabilizer for a hydrazine compound selected from hydrazine and hydrazine hydrate, characterized in that the active ingredient is one or more surfactants selected from sulfonates. 2. The stabilizer for a hydrazine compound according to claim 1, wherein the hydrazine compound is used for water treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6198783A JPS59189185A (en) | 1983-04-08 | 1983-04-08 | Stabilizer for hydrazine compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6198783A JPS59189185A (en) | 1983-04-08 | 1983-04-08 | Stabilizer for hydrazine compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59189185A JPS59189185A (en) | 1984-10-26 |
JPS6327284B2 true JPS6327284B2 (en) | 1988-06-02 |
Family
ID=13187042
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6198783A Granted JPS59189185A (en) | 1983-04-08 | 1983-04-08 | Stabilizer for hydrazine compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59189185A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4023383A1 (en) * | 1989-07-24 | 1991-01-31 | United Technologies Corp | METHOD FOR IMPROVING THE THERMAL STABILITY OF HYDROCARBON FUELS |
JP3755543B2 (en) * | 1995-08-14 | 2006-03-15 | 三菱瓦斯化学株式会社 | Method for producing hydrated hydrazine |
WO2000005946A1 (en) * | 1998-07-29 | 2000-02-10 | Kao Corporation | Freshness-keeping agents for plants |
EP2655249A1 (en) * | 2010-12-21 | 2013-10-30 | Cytec Technology Corp. | Processes for removing hydrazine form hydroxylamine solutions |
-
1983
- 1983-04-08 JP JP6198783A patent/JPS59189185A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS59189185A (en) | 1984-10-26 |
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