JPH0637622B2 - Neutralizer for oil refining or petroleum process - Google Patents
Neutralizer for oil refining or petroleum processInfo
- Publication number
- JPH0637622B2 JPH0637622B2 JP61157486A JP15748686A JPH0637622B2 JP H0637622 B2 JPH0637622 B2 JP H0637622B2 JP 61157486 A JP61157486 A JP 61157486A JP 15748686 A JP15748686 A JP 15748686A JP H0637622 B2 JPH0637622 B2 JP H0637622B2
- Authority
- JP
- Japan
- Prior art keywords
- petroleum
- corrosion
- present
- neutralizing agent
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は石油精製又は石油プロセス用中和剤に係り、特
に石油精製装置の腐食防止、例えば石油蒸留装置の初期
水凝縮箇所で起こる酸腐食の防止、あるいは石油プロセ
スにおける酸腐食や中和塩による弊害を防止するに好適
な中和剤に関する。Description: TECHNICAL FIELD The present invention relates to a neutralizing agent for petroleum refining or a petroleum process, and particularly to corrosion protection of a petroleum refining apparatus, for example, acid corrosion occurring at an initial water condensation point of a petroleum distilling apparatus. The present invention relates to a neutralizing agent suitable for preventing the above, or for preventing the harmful effects of acid corrosion and neutralizing salts in petroleum processes.
［従来の技術］ 石油精製、石油化学プロセスにおいては、原油中に含ま
れて系内に持ち込まれる酸性物質や、プロセス内で生成
する酸性物質、例えばＨ２Ｓ、ＨＣＮ、ＣＯ２、ＨＣ
等によって、原油塔のような塔内トレー、熱交換器、受
容タンク、連結パイプ等の各装置の系内の金属表面上で
pH低下による激しい酸腐食が発生する。[Prior Art] In petroleum refining and petrochemical processes, acidic substances contained in crude oil and introduced into the system, and acidic substances generated in the process, such as H 2 S, HCN, CO 2 , and HC.
On the metal surface in the system of each equipment such as tower in the tower such as crude oil tower, heat exchanger, receiving tank, connecting pipe, etc.
Severe acid corrosion occurs due to pH decrease.
例えば、原油の常圧蒸留装置では、原油中に含まれる塩
化マグネシウムや塩化カルシウムなどが、加熱により加
水分解して塩化水素を発生し、このため、塔頂系でドレ
ン水のpHを著しく低下させ、激しい腐食が発生する。特
に、水分が最初に凝縮する凝縮器中及び分留塔から通じ
ている塔頂部管路中においては極めて厳しい腐食がおこ
る。For example, in an atmospheric distillation apparatus for crude oil, magnesium chloride, calcium chloride, etc. contained in the crude oil are hydrolyzed by heating to generate hydrogen chloride, which significantly reduces the pH of drain water in the overhead system. , Severe corrosion occurs. In particular, extremely severe corrosion occurs in the condenser where the water first condenses and in the top line leading from the fractionating tower.
このような酸腐食は、石油精製装置に限らず、石油化学
プロセスにおいて起こり、例えばＢＴＸ精製プロセスで
はトッパーを用いて精製するものであるが、同様の問題
が生ずる。それ以外でも、塩ビモノマー製造プラント等
においては、原料の塩化水素とエチレンからエチレンジ
クロライドを合成し、脱塩酸したのち塩ビモノマーを製
造するが、系内に各種の塩化物が生成し、精製工程で微
量の塩酸が発生して、酸腐食をひきおこすとともに精製
が困難となる場合がある。Such acid corrosion occurs not only in petroleum refining equipment but also in petrochemical processes. For example, in the BTX refining process, refining is performed using a topper, but similar problems occur. Other than that, in a vinyl chloride monomer production plant, etc., ethylene dichloride is synthesized from raw material hydrogen chloride and ethylene, and after dehydrochlorination, a vinyl chloride monomer is produced, but various chlorides are generated in the system, and in the purification process. A slight amount of hydrochloric acid may be generated, causing acid corrosion and making purification difficult.
このため、従来より、酸による腐食やその他の弊害を防
止、抑制するために、アンモニア、モルホリン、エチレ
ンジアミンやピペラジン（特公昭５２−３８９８）、モ
ノ又はイソプロパノールアミン（特公昭５３−４７２４
１）を系内に注入する方法が採用されていた。Therefore, conventionally, in order to prevent or suppress corrosion due to acid and other adverse effects, ammonia, morpholine, ethylenediamine, piperazine (Japanese Patent Publication No. 52-3898), mono- or isopropanolamine (Japanese Patent Publication No. 53-4724).
The method of injecting 1) into the system has been adopted.
［発明が解決しようとする問題点］ しかしながら、アンモニアは例えば石油精製装置の蒸留
装置初期凝縮部の腐食抑制のために、塔頂配管に注入し
た場合、塩化水素は水側に移行しやすいが、アンモニア
は移行せずまた気相で反応して水側に移行した塩化アン
モニウムは加水分解されてアンモニアが放出され、凝縮
水のpHを低下させ、金属面を腐食させる。このように、
アンモニアは初期凝縮部への移行性が悪いことから、初
期凝縮部の腐食を抑制するには不適当である。[Problems to be solved by the invention] However, for example, when ammonia is injected into the overhead piping for the purpose of suppressing corrosion of the initial condensation section of the distillation apparatus of the oil refinery, hydrogen chloride tends to move to the water side, Ammonia does not move and ammonium chloride that has moved to the water side by reacting in the gas phase is hydrolyzed and ammonia is released, lowering the pH of the condensed water and corroding the metal surface. in this way,
Ammonia is not suitable for suppressing the corrosion of the initial condensation part because it has a poor transfer property to the initial condensation part.
一方、モルホリン、エチレンジアミンやピベラジンは、
初期凝縮部への移行性は良好で、pHを上昇させて腐食を
抑制することができるが、中和により生成するアミン塩
酸塩の融点が高いため、蒸留カラム、カラムポンプ周
辺、塔頂部管路や熱交換器中で沈積し、配管系の目詰り
や塩類による二次腐食の発生をひきおこすという問題が
ある。また、生成したアミン塩酸塩の熱分解温度が比較
的低いことから、捕捉した塩酸が熱分解により再度放出
されるという問題もあった。On the other hand, morpholine, ethylenediamine and piberazine are
The transferability to the initial condensation part is good, and corrosion can be suppressed by raising the pH, but since the amine hydrochloride generated by neutralization has a high melting point, the distillation column, the column pump area, and the top pipe line However, there is a problem in that it accumulates in the heat exchanger and causes clogging of the piping system and secondary corrosion due to salts. Further, since the generated amine hydrochloride has a relatively low thermal decomposition temperature, there is a problem that the captured hydrochloric acid is released again by thermal decomposition.
更にモノ，イソプロパノールアミンでは、移行性は良好
で、そのアミン塩酸塩の融点もエチレンジアミン等のア
ミン塩酸塩と比べると低く、目詰り等の問題はかなり低
減されるが、水溶解度が比較的低いため、目詰りの問題
は解消されず、また、アミン塩酸塩の熱分解温度が比較
的低く、一部が熱分解をうけて塩酸を再度放出する等の
問題がある。Furthermore, with mono- and isopropanolamine, migration is good, and the melting point of the amine hydrochloride is lower than amine hydrochlorides such as ethylenediamine, and problems such as clogging are considerably reduced, but the solubility in water is relatively low. However, the problem of clogging is not solved, and the thermal decomposition temperature of amine hydrochloride is relatively low, and there is a problem that hydrochloric acid is released again due to partial thermal decomposition.
［問題点を解決するための手段］ 本発明者らは、上記従来の問題点を解決すべく鋭意検討
を重ねた結果、初期凝縮部への移行性が良好で優れた腐
食抑制効果を有し、形成されているアミン塩酸塩の沈積
又は分解による塩酸の再放出等の問題もない中和剤アミ
ンを見出し、本発明を完成させた。[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above-mentioned conventional problems, and as a result, have good transferability to the initial condensation part and have an excellent corrosion inhibition effect. The present invention has been completed by finding a neutralizer amine that does not cause problems such as re-release of hydrochloric acid due to the deposition or decomposition of the formed amine hydrochloride.
即ち、本発明は メチルエタノールアミン、メチルジエタノールアミン、
エチルエタノールアミン及びエチルジエタノールアミン
から成る群から選ばれる少なくとも１種のアルカノール
アミンを含むことを特徴とする石油精製又は石油プロセ
ス用中和剤、 を要旨とするものである。That is, the present invention is methylethanolamine, methyldiethanolamine,
A neutralizing agent for petroleum refining or a petroleum process, comprising at least one alkanolamine selected from the group consisting of ethylethanolamine and ethyldiethanolamine.
以下に本発明を詳細に説明する。The present invention will be described in detail below.
本発明の石油精製又は石油プロセス用中和剤は、メチル
エタノールアミン、メチルジエタノールアミン、エチル
エタノールアミン及びエチルジエタノールアミンから成
る群から選ばれる１種又は２種以上のアルカノールアミ
ンを有効成分として含有するものである。The neutralizing agent for petroleum refining or petroleum process of the present invention contains, as an active ingredient, one or more alkanolamines selected from the group consisting of methylethanolamine, methyldiethanolamine, ethylethanolamine and ethyldiethanolamine. is there.
本発明の中和剤は、対象油中にそのまま注入しても良
く、予め水等で溶解してから注入しても良い。その注入
量は、処理対象によっても異なるが、例えば石油精製装
置の初期凝縮部においては、その初期凝縮部の水分のpH
を約４．０、好ましくは約５．０以上まで上げるのに十
分な量とするのが好ましい。The neutralizing agent of the present invention may be directly injected into the target oil, or may be previously dissolved in water or the like and then injected. Although the injection amount varies depending on the processing target, for example, in the initial condensation section of a petroleum refinery, the pH of water in the initial condensation section is
To about 4.0, preferably about 5.0 or more.
注入方法は、連続注入でも間欠注入でも良いが、通常、
連続注入が好ましく、対象油中に均一に分散するように
充分攪拌しながら注入するのが特に好ましい。The injection method may be continuous injection or intermittent injection, but normally,
Continuous injection is preferable, and it is particularly preferable to inject with sufficient stirring so that the oil is uniformly dispersed in the target oil.
添加場所としては、常温蒸留装置の場合にはトッパーの
サイドリフラックスラインやトップリフラックスライン
等が効率的な場所として例示できる。一方、前述した塩
ビモノマー製造プラントの場合には、塩ビモノマー塔の
フィードライン等に注入すれば良い。即ち、本発明の中
和剤は、石油系プラントにおいて、熱負荷がかかる系内
やその直前、あるいは環流系へ添加するのが有効であ
る。In the case of a room temperature distillation apparatus, a side reflux line or a top reflux line of a topper can be exemplified as an efficient place of addition. On the other hand, in the case of the above-mentioned vinyl chloride monomer production plant, it may be injected into the feed line of the vinyl chloride monomer tower or the like. That is, it is effective that the neutralizing agent of the present invention is added to a system under heat load in a petroleum-based plant, immediately before the system, or to a reflux system.
なお、本発明は必要に応じて他の皮膜性アミンや従来よ
り公知の中和剤を併用して用いることもできる。In the present invention, other film-forming amines or conventionally known neutralizing agents can be used in combination, if necessary.
［作用］ メチルエタノールアミン、メチルジエタノールアミン、
エチルエタノールアミン及びエチルジエタノールアミン
は、初期凝縮部への移行性がよく、初期凝縮水のpHを上
昇させることができるばかりでなく、中和により生成す
るアミン塩酸塩の融点が低くかつ水溶解度が大きいた
め、蒸留カラム、カラムポンプ周辺、塔頂部管路又は塔
頂部熱交換器中で沈積して目詰りや塩類により二次腐食
を発生することもない。[Function] Methylethanolamine, methyldiethanolamine,
Ethylethanolamine and ethyldiethanolamine have good transferability to the initial condensation part and can not only raise the pH of the initial condensed water, but also have a low melting point and high water solubility of the amine hydrochloride formed by neutralization. Therefore, the secondary corrosion does not occur due to clogging and salts due to sedimentation in the distillation column, around the column pump, in the overhead pipe or the overhead heat exchanger.
このため、本発明の中和剤によれば、石油精製又は石油
プロセスにおける酸による腐食あるいはその他の弊害を
極めて効率的に抑制ないし防止することができる。Therefore, according to the neutralizing agent of the present invention, it is possible to extremely effectively suppress or prevent corrosion due to acid or other adverse effects in petroleum refining or petroleum processes.
［実施例］ 以下に実施例を挙げて本発明をより具体的に説明する
が、本発明はその要旨を超えない限り以下の実施例に限
定されるものではない。[Examples] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
実施例１ 第１図に示す試験装置を用いて本発明の中和剤の性能実
験を行なった。Example 1 A performance test of the neutralizing agent of the present invention was conducted using the test apparatus shown in FIG.
試験液として塩酸５０mg／、酢酸１００mg／及び硫
化水素５０mg／を含む蒸留水を用意し、３９０g/hrの
速度で加熱部１に注入した。加熱部１では２５０〜３０
０℃となるように試験液を加熱した。加熱によって気化
した蒸気は塔頂部で１３０℃前後となるように保温ヒー
タ２付きのカラム部３へ導通させた。そして、塔頂部か
ら表１に示す本発明の各種中和剤アミン溶液を最終凝縮
水のpHが６．０となるように所定量添加した。次に蒸気
を初期凝縮部４へ送り、７８℃まで冷やし、凝縮率が１
０％となるようにした。そして最終的に水で冷却して残
り全量を最終凝縮水として回収した。Distilled water containing hydrochloric acid 50 mg /, acetic acid 100 mg /, and hydrogen sulfide 50 mg / was prepared as a test solution, and poured into the heating part 1 at a rate of 390 g / hr. 250-30 in heating unit 1
The test solution was heated to 0 ° C. The steam vaporized by heating was conducted to the column section 3 equipped with the heat retention heater 2 so that the temperature was around 130 ° C. at the tower top. Then, from the top of the column, various neutralizing agent amine solutions of the present invention shown in Table 1 were added in predetermined amounts so that the pH of the final condensed water was 6.0. Next, the steam is sent to the initial condensing section 4 and cooled to 78 ° C., and the condensation rate becomes 1
It was set to 0%. Finally, it was cooled with water and the whole remaining amount was recovered as final condensed water.
なお、配管は全て保温配管とした。In addition, all the piping was heat retention piping.
用いた中和剤及び試験結果を表１に示す。Table 1 shows the neutralizing agent used and the test results.
なお、１０％凝縮水のpHは初期凝縮水をpH計で、また、
初期凝縮部カラム付着量は、初期凝縮部の壁面に付着し
たアミン塩酸塩の量を測定したものである。In addition, the pH of the 10% condensed water is the initial condensed water measured with a pH meter.
The initial condensation section column adhesion amount is a measurement of the amount of amine hydrochloride adhering to the wall surface of the initial condensation section.
また、比較のためにアンモニア、モルホリン、エチレン
ジアミン、ジメチルアミンエタノール（ＤＭＡＥ）、ジ
メチルイソプロパノールアミン（ＤＭＰＡ）及びモノイ
ソプロパノールアミンについても同様な試験を行ない、
結果を表１に示した。Also, for comparison, the same test was conducted on ammonia, morpholine, ethylenediamine, dimethylamine ethanol (DMAE), dimethylisopropanolamine (DMPA) and monoisopropanolamine,
The results are shown in Table 1.
表１より、本発明の中和剤は初期凝縮部のpHを十分に上
昇させることができると共に、凝縮部のカラム付着量が
極めて少ないことがわかる。 It can be seen from Table 1 that the neutralizing agent of the present invention can sufficiently raise the pH of the initial condensation part and that the amount of column adhesion to the condensation part is extremely small.
実施例２ 実施例１で用いた試験装置において、初期凝縮部カラム
内に軟鋼（ＳＴＰＧ）製テストピース（表面積１９c
m2）を懸垂させた以外は全く同様の操作を行なった。Example 2 In the test apparatus used in Example 1, a mild steel (STPG) test piece (surface area 19 c
The same operation was performed except that m 2 ) was suspended.
結果を表２に示す。なお、腐食率はテストピースの腐食
減量から算出した。The results are shown in Table 2. The corrosion rate was calculated from the corrosion weight loss of the test piece.
表２より本発明の中和剤が優れた防食効果を発揮するこ
とがわかる。Table 2 shows that the neutralizing agent of the present invention exhibits an excellent anticorrosion effect.
［発明の効果］ 以上詳述した通り、本発明の石油精製又は石油プロセス
用中和剤は、メチルエタノールアミン、メチルジエタノ
ールアミン、エチルエタノールアミン及びエチルジエタ
ノールアミンよりなる群から選ばれる１種以上を含むも
のであって、初期凝縮部への移行性が良く、石油蒸留装
置の最初の水凝縮箇所で起こる酸腐食も十分に抑制する
ことができる。しかも、中和により生成するアミン塩酸
塩は融点が低く、水溶解度が大きいため、アミン塩酸塩
による系内の目詰りや二次腐食を起こすことがない。 [Effects of the Invention] As described in detail above, the neutralizing agent for petroleum refining or petroleum processes of the present invention contains at least one member selected from the group consisting of methylethanolamine, methyldiethanolamine, ethylethanolamine and ethyldiethanolamine. However, the transferability to the initial condensation part is good, and the acid corrosion that occurs at the first water condensation part of the petroleum distillation apparatus can be sufficiently suppressed. Moreover, since the amine hydrochloride produced by neutralization has a low melting point and a high water solubility, clogging of the system and secondary corrosion due to the amine hydrochloride do not occur.
このため、本発明の中和剤によれば、各種石油精製系又
は石油プロセス系において、中和による弊害を生起する
ことなく、酸による腐食あるいはその他の問題も極めて
効率的に抑制ないし防止することができる。Therefore, according to the neutralizing agent of the present invention, in various petroleum refining systems or petroleum process systems, the corrosion due to acid or other problems can be extremely efficiently suppressed or prevented without causing any adverse effects due to neutralization. You can
第１図は実施例１及び２で用いた試験装置を示す系統図
である。 １……加熱部、２……保温ヒータ、 ３……カラム部、４……初期凝縮部。FIG. 1 is a system diagram showing the test apparatus used in Examples 1 and 2. 1 ... Heating part, 2 ... Insulating heater, 3 ... Column part, 4 ... Initial condensation part.
Claims (1)
ールアミン、エチルエタノールアミン及びエチルジエタ
ノールアミンから成る群から選ばれる少なくとも１種の
アルカノールアミンを含むことを特徴とする石油精製又
は石油プロセス用中和剤。1. A neutralizing agent for petroleum refining or a petroleum process comprising at least one alkanolamine selected from the group consisting of methylethanolamine, methyldiethanolamine, ethylethanolamine and ethyldiethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61157486A JPH0637622B2 (en) | 1986-07-04 | 1986-07-04 | Neutralizer for oil refining or petroleum process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61157486A JPH0637622B2 (en) | 1986-07-04 | 1986-07-04 | Neutralizer for oil refining or petroleum process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6315886A JPS6315886A (en) | 1988-01-22 |
| JPH0637622B2 true JPH0637622B2 (en) | 1994-05-18 |
Family
ID=15650731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61157486A Expired - Fee Related JPH0637622B2 (en) | 1986-07-04 | 1986-07-04 | Neutralizer for oil refining or petroleum process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637622B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9493715B2 (en) | 2012-05-10 | 2016-11-15 | General Electric Company | Compounds and methods for inhibiting corrosion in hydrocarbon processing units |
| US9297081B2 (en) * | 2014-02-21 | 2016-03-29 | Ecolab Usa Inc. | Use of neutralizing agent in olefin or styrene production |
| TWI591054B (en) | 2015-07-29 | 2017-07-11 | 藝康美國公司 | Heavy amine neutralizing agents for olefin or styrene production |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382855A (en) | 1981-10-28 | 1983-05-10 | Ashland Oil, Inc. | Process for removal of hydroxy- and/or mercapto-substituted hydrocarbons from coal liquids |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS526704A (en) * | 1975-07-07 | 1977-01-19 | Kurita Water Ind Ltd | Neutralizing agent for crude oil |
| US4430196A (en) * | 1983-03-28 | 1984-02-07 | Betz Laboratories, Inc. | Method and composition for neutralizing acidic components in petroleum refining units |
-
1986
- 1986-07-04 JP JP61157486A patent/JPH0637622B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382855A (en) | 1981-10-28 | 1983-05-10 | Ashland Oil, Inc. | Process for removal of hydroxy- and/or mercapto-substituted hydrocarbons from coal liquids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6315886A (en) | 1988-01-22 |
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