JPS6248558B2 - - Google Patents
Info
- Publication number
- JPS6248558B2 JPS6248558B2 JP56137175A JP13717581A JPS6248558B2 JP S6248558 B2 JPS6248558 B2 JP S6248558B2 JP 56137175 A JP56137175 A JP 56137175A JP 13717581 A JP13717581 A JP 13717581A JP S6248558 B2 JPS6248558 B2 JP S6248558B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- drain water
- hydrogen sulfide
- copolymer
- water
- 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 32
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 11
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002519 antifouling agent Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005504 petroleum refining Methods 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FZQMZRXKWHQJAG-VOTSOKGWSA-N (e)-3,4,4-trimethylpent-2-ene Chemical compound C\C=C(/C)C(C)(C)C FZQMZRXKWHQJAG-VOTSOKGWSA-N 0.000 description 1
- SZFRZEBLZFTODC-UHFFFAOYSA-N 2,3,4-trimethylpent-2-ene Chemical compound CC(C)C(C)=C(C)C SZFRZEBLZFTODC-UHFFFAOYSA-N 0.000 description 1
- LAAVYEUJEMRIGF-UHFFFAOYSA-N 2,4,4-trimethylpent-2-ene Chemical compound CC(C)=CC(C)(C)C LAAVYEUJEMRIGF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】
この発明は石油精製プロセスから排出される硫
化水素を含むドレン水を処理する系において、汚
れを防止する薬剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agent for preventing fouling in a system for treating drain water containing hydrogen sulfide discharged from a petroleum refining process.
石油の精製は、常圧蒸留法、減圧蒸留法、接触
分解法、接触改質法などによつてなされるが、い
ずれの方法においても、蒸気や水洗水が用いら
れ、石油精製プロセスの油水分離からは硫化水素
を含む水が排出される。このドレン水は通常スチ
ームストリツパーにより硫化水素やアンモニアな
どを含むいわゆるサワーガスを除去したのち、水
洗水や他の雑用水に使用されているが、スチーム
ストリツパーの前の熱交換器の内部、スチームス
トリツパーのトレイおよびストレイナーなどに油
分をバインダーとした硫化鉄を主成分とする汚れ
が付着し、伝熱効率の低下や閉塞などの問題があ
つた。特に伝熱効率の低下は、スチームエネルギ
ーの使用増大を招くので、改善が求められてい
た。 Petroleum is refined by atmospheric distillation, vacuum distillation, catalytic cracking, catalytic reforming, etc. All of these methods use steam and washing water, and are used to separate oil and water in the oil refining process. Water containing hydrogen sulfide is discharged from the plant. This drain water is usually used as washing water or other miscellaneous water after removing so-called sour gas containing hydrogen sulfide and ammonia using a steam stripper. , stains mainly composed of iron sulfide with oil as a binder adhered to steam stripper trays and strainers, causing problems such as reduced heat transfer efficiency and blockages. In particular, a decrease in heat transfer efficiency leads to an increase in the use of steam energy, so improvements have been sought.
本発明はこのような状況下に、石油精製プロセ
スから排出される硫化水素を含むドレン水を処理
する系の油分をバインダーとした硫化鉄を主成分
とする汚れを防止する薬剤を提供することを目的
とする。すなわち、本発明は、石油精製プロセス
の硫化水素を含むドレン水処理系の油分をバイン
ダーとした硫化鉄を主成分とする汚れを防止する
薬剤であつて、構成単位としてジイソブチレン
と、マレイン酸とを含む共重合体を有効成分とし
て含有することを特徴とする石油精製プロセスの
硫化水素を含むドレン水処理系の汚れ防止剤であ
る。 Under such circumstances, the present invention aims to provide a stain-preventing agent containing iron sulfide as a main component and using oil from a system for treating drain water containing hydrogen sulfide discharged from an oil refining process as a binder. purpose. That is, the present invention is a stain-preventing agent mainly composed of iron sulfide, which uses oil from a drain water treatment system containing hydrogen sulfide in an oil refining process as a binder, and which contains diisobutylene and maleic acid as constituent units. This is an antifouling agent for drain water treatment systems containing hydrogen sulfide in petroleum refining processes, characterized by containing a copolymer containing as an active ingredient.
ジイソブチレンはイソブチレンを接触重合して
得られる二量体であり、２・４・４−トリメチル
−１−ペンテン、２・４・４−トリメチル−２−
ペンテン、２・３・４−トリメチル−２−ペンテ
ン、３・４・４−トリメチル−２−ペンテンまた
はこれらの混合物が含まれる。マレイン酸には、
マレイン酸塩や無水マレイン酸が含まれる。本発
明の共重合体には、これらの構造単位と重合可能
な他の構造単位が共重合していてもよい。例えば
無水マレイン酸とジイソブチレンの共重合体にア
ンモニアを反応させて無水マレイン酸の構造単位
を部分的にアミド化してもよい。 Diisobutylene is a dimer obtained by catalytic polymerization of isobutylene, and includes 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-
Pentene, 2,3,4-trimethyl-2-pentene, 3,4,4-trimethyl-2-pentene or mixtures thereof. Maleic acid has
Contains maleate salts and maleic anhydride. In the copolymer of the present invention, these structural units and other polymerizable structural units may be copolymerized. For example, a copolymer of maleic anhydride and diisobutylene may be reacted with ammonia to partially amidate the structural units of maleic anhydride.
ジイソブチレンとマレイン酸とのモル比は１：
９〜９：１好ましくは１：４〜４：１であるが、
特に１：１が好ましい。共重合体の分子量は1000
〜50000好ましくは1000〜10000である。1000未満
または50000を越えると汚れ防止効果が顕著でな
くなる。 The molar ratio of diisobutylene and maleic acid is 1:
9 to 9:1, preferably 1:4 to 4:1,
Particularly preferred is 1:1. The molecular weight of the copolymer is 1000
~50000 preferably 1000-10000. If it is less than 1,000 or more than 50,000, the stain prevention effect will not be significant.
上記共重合体の製法としては、溶液重合、懸濁
重合、乳化重合などの常法が挙げられるが、無水
マレイン酸とジイソブチレンとをベンゼン、トル
エンなどの有機溶媒中で交互共重合して製造する
ことが好ましい。 The above copolymer can be produced by conventional methods such as solution polymerization, suspension polymerization, and emulsion polymerization, but it is produced by alternately copolymerizing maleic anhydride and diisobutylene in an organic solvent such as benzene or toluene. It is preferable to do so.
本発明の共重合体は、そのままドレン水中に添
加して使用することができるが、ナトリウム塩、
カリウム塩等のアルカリ金属塩やアンモニウム塩
などの水溶性塩の形に使用すると水に対する溶解
性を高めることができ、好ましい。添加の仕方と
しては、原液そのまま添加することもできるが、
水で希釈して注入すると、均一に分散させること
ができ好ましい。添加場所としては、熱交換器や
スチームストリツパーの入口が適当である。添加
量は、通常ドレン水量に対し、共重合体として１
mg／以上好ましくは５mg／以上とし、ドレン
水中の油状成分量やSS（懸濁固形物）量によつ
て適宜増減する。 The copolymer of the present invention can be used as it is by being added to drain water, but sodium salt,
It is preferable to use it in the form of an alkali metal salt such as a potassium salt or a water-soluble salt such as an ammonium salt, since the solubility in water can be increased. As for how to add, it is possible to add the undiluted solution as it is, but
It is preferable to dilute it with water and then inject it because it allows uniform dispersion. Suitable addition locations include the inlet of a heat exchanger or steam stripper. The amount added is usually 1% of the copolymer to the amount of drain water.
mg/or more, preferably 5 mg/or more, and may be increased or decreased as appropriate depending on the amount of oily components and the amount of SS (suspended solids) in the drain water.
本発明の薬剤を適用することのできるドレン水
の例を挙げると、常圧蒸留法における蒸留塔およ
びスタビライザーの凝縮液から油水分離されたド
レン水、減圧蒸留法における蒸留塔の凝縮液から
油水分離されたドレン水、接触分解法における精
留塔の凝縮液から油水分離されたドレン水、およ
び接触改質法におけるスタビライザーの凝縮液か
ら油水分離されたドレン水などがあるが、これに
限定されない。これらのドレン水中には、油分、
硫化水素、メルカプタン、および石油中の硫化物
と石油精製装置の鉄分とが反応してできる硫化鉄
が含まれており、油分が硫化鉄のバインダーとな
つて汚れとなる。本発明の汚れ防止剤はドレン水
中に添加されると、油分が硫化鉄のバインダーと
なるのを抑制し、また硫化鉄の粒子を沈殿させる
ことなく分散させる。したがつて、従来は汚れの
ため伝熱効率が低下し蒸気が有効に利用されなか
つたり、また汚れ除去のための装置の運転を停め
てたびたび洗浄しなければならなかつたが、本発
明により汚れの付着が防止でき、操業時間を大巾
に延ばすことができると共に貴重な蒸気を有効に
利用することができる。 Examples of drain water to which the agent of the present invention can be applied include drain water separated from oil and water from the condensate of a distillation column and stabilizer in the atmospheric distillation method, and oil and water separated from the condensate of the distillation column in the vacuum distillation method. Drain water separated from oil and water from the condensate of a rectification column in a catalytic cracking method, drain water separated from oil and water from a condensate of a stabilizer in a catalytic reforming method, but is not limited thereto. These drain water contains oil,
It contains hydrogen sulfide, mercaptans, and iron sulfide, which is formed when the sulfide in petroleum reacts with the iron in oil refinery equipment, and the oil acts as a binder for the iron sulfide, resulting in dirt. When added to drain water, the antifouling agent of the present invention prevents oil from becoming a binder for iron sulfide and disperses iron sulfide particles without precipitating them. Therefore, in the past, heat transfer efficiency was reduced due to contamination, steam was not used effectively, and the operation of the contamination removal equipment had to be stopped and cleaned frequently, but with the present invention, contamination removal Adhesion can be prevented, operating time can be greatly extended, and valuable steam can be used effectively.
次に本発明の汚れ防止剤の効果を実施例を挙げ
て説明する。 Next, the effect of the antifouling agent of the present invention will be explained with reference to Examples.
実施例
硫化水素を約1000mg／含む水をアンモニアで
PH９としたのち、汚れ防止剤を添加し、これを直
径25mm、高さ200mmのガラス製沈降管に入れ、恒
温水槽中で80℃に保つた。次に石油精製工業のド
レン水ストリツパーのトレイに生成した付着物を
粉砕して、その約0.1ｇを恒温水槽から取り出し
たガラス製沈降管に加え50rpmで３分間転倒撹拌
したのち、再び恒温水槽中に戻して静置し、観察
した。汚れ防止剤としてジイソブチレンと無水マ
レイン酸とのモル比１対１の共重合体（分子量約
１万）を１mg／添加した場合付着物粒子は約30
分間、分散状態を示し、10mg／添加した場合は
１時間以上分散状態が持続した。薬剤無添加の場
合は、５分後に付着物粒子のほとんどが沈降し
た。また汚れ防止剤としてイソブチレンと無水マ
レイン酸とのモル比１対１の共重合体（分子量約
1.4万）を１mg／添加した場合、付着物粒子は
10分間分散状態を示したが、いずれもその後付着
物粒子のほとんどが沈降した。Example: Water containing approximately 1000 mg of hydrogen sulfide was mixed with ammonia.
After adjusting the pH to 9, an antifouling agent was added, and the mixture was placed in a glass sedimentation tube with a diameter of 25 mm and a height of 200 mm, and kept at 80°C in a constant temperature water bath. Next, the deposits formed on the tray of a drain water stripper in the oil refinery industry were pulverized, and about 0.1 g of this was added to the glass sedimentation tube taken out from the constant temperature water bath, and after stirring at 50 rpm for 3 minutes, it was placed in the constant temperature water bath again. I returned it to the room, allowed it to stand still, and observed it. When 1 mg of a copolymer of diisobutylene and maleic anhydride (molecular weight approximately 10,000) with a molar ratio of 1:1 is added as a stain preventive agent, the amount of deposit particles is approximately 30.
It remained in a dispersed state for 1 minute, and the dispersed state continued for more than 1 hour when 10 mg/dose was added. In the case where no drug was added, most of the deposit particles settled out after 5 minutes. In addition, as an antifouling agent, a copolymer of isobutylene and maleic anhydride in a molar ratio of 1:1 (molecular weight approx.
14,000), the deposit particles are
Although a dispersed state was observed for 10 minutes, most of the deposit particles settled after that time.
Claims (1)
処理系の油分をバインダーとした硫化水素を主成
分とする汚れを防止する薬剤であつて、構造単位
としてジイソブチレンと、マレイン酸とを含む共
重合体を有効成分として含有することを特徴とす
る石油精製プロセスの硫化水素を含むドレン水処
理系の汚れ防止剤。 ２ 共重合体の分子量は1000〜50000である特許
請求の範囲第１項記載の汚れ防止剤。[Scope of Claims] 1. A stain-preventing agent containing hydrogen sulfide as a main component and using as a binder oil from a drain water treatment system containing hydrogen sulfide in an oil refining process, which contains diisobutylene and maleic acid as structural units. An antifouling agent for drain water treatment systems containing hydrogen sulfide in petroleum refining processes, characterized by containing a copolymer containing as an active ingredient. 2. The antifouling agent according to claim 1, wherein the copolymer has a molecular weight of 1,000 to 50,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13717581A JPS5840199A (en) | 1981-09-01 | 1981-09-01 | Antifouling agent for treating system of hydrogen sulfide-contg. drain in petroleum-refining process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13717581A JPS5840199A (en) | 1981-09-01 | 1981-09-01 | Antifouling agent for treating system of hydrogen sulfide-contg. drain in petroleum-refining process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5840199A JPS5840199A (en) | 1983-03-09 |
| JPS6248558B2 true JPS6248558B2 (en) | 1987-10-14 |
Family
ID=15192562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13717581A Granted JPS5840199A (en) | 1981-09-01 | 1981-09-01 | Antifouling agent for treating system of hydrogen sulfide-contg. drain in petroleum-refining process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5840199A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538869A (en) * | 1991-08-07 | 1993-02-19 | Seiko Instr Inc | End detecting method for color ink sheet film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5420194A (en) * | 1994-02-14 | 1995-05-30 | Nalco Chemical Company | αolefin/maelic anhydride copolymers as antifoulants in ethylene process water stripper systems |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53146279A (en) * | 1977-05-26 | 1978-12-20 | Kurita Water Ind Ltd | Corrosion, scale, and stain inhibitor in aqueous system |
-
1981
- 1981-09-01 JP JP13717581A patent/JPS5840199A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53146279A (en) * | 1977-05-26 | 1978-12-20 | Kurita Water Ind Ltd | Corrosion, scale, and stain inhibitor in aqueous system |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538869A (en) * | 1991-08-07 | 1993-02-19 | Seiko Instr Inc | End detecting method for color ink sheet film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5840199A (en) | 1983-03-09 |
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