JP3381273B2 - Antifouling agent for petroleum refining - Google Patents
Antifouling agent for petroleum refiningInfo
- Publication number
- JP3381273B2 JP3381273B2 JP21067392A JP21067392A JP3381273B2 JP 3381273 B2 JP3381273 B2 JP 3381273B2 JP 21067392 A JP21067392 A JP 21067392A JP 21067392 A JP21067392 A JP 21067392A JP 3381273 B2 JP3381273 B2 JP 3381273B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- antifouling agent
- petroleum refining
- formula
- oil
- 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 - Lifetime
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【発明の詳細な説明】
【0001】
【産業上の利用分野】本発明は、石油精製装置における
汚れの付着を防止する石油精製用汚れ防止剤に関する。
【0002】
【従来の技術】石油精製工業において、最近は環境問題
への対応や白油増産の観点から、精製設備の高度化が図
られており、特に重質油留分の処理では水素化分解装
置、水素化脱硫装置、接触分解装置等の導入、あるいは
これらの装置の運転条件の苛酷化が進められている。こ
れらの装置の導入あるいは運転条件の苛酷化により、こ
れらの装置から得られる残油中にスラッジが生成し、熱
交換器の汚れやフィルターの閉塞等の障害を引き起こ
す。このような障害が生じた場合には装置の運転を停止
し汚れ付着物を除去する作業を行うが、この作業を頻繁
に行うことは、プラントの停止に繋る。このような事態
を回避するために運転条件の緩和あるいは装置の並列化
などを行うが、これらは経済的に極めて不利なものであ
る。
【0003】汚れ物質の付着を防止するために、従来よ
り供給原料に汚れ防止剤を添加する多くの方法が提案さ
れている。斯かる汚れ防止剤としては、例えば高分子量
(分子量600〜3000)モノカルボン酸とアルキレンポリ
アミンとのアミド縮合生成物(特公昭46−23504 号公
報) 、アンモニア(特開昭54−69106 号公報)、ポリア
ルキレンアミン(特開昭55−129490号公報) 、ポリオキ
シアルキレンカルバメート(特開昭59−232170号公報)
などがある。しかし、これらの化合物を原油などの供給
原料に添加することにより、ある程度汚れの付着を防止
することができるが、まだ十分なものではない。
【0004】
【発明が解決しようとする課題】本発明は、石油精製工
程において、熱交換器および各種処理装置の汚れの付着
を防止する高性能な汚れ防止剤を提供することを目的と
するものである。
【0005】
【課題を解決するための手段】本発明者らは、鋭意研究
を行った結果、アルキルアルキレンジアミンのアミド化
合物が汚れ防止剤として有効であることを見出し、本発
明を完成した。すなわち、本発明は下記の式(A)で表
される化合物と式(B)で表される化合物とのモル比2
/1〜4/5での反応生成物であるアルキルアルキレン
ジアミンのアミド化合物を有効成分とする石油精製用汚
れ防止剤である。
【0006】
R1COOH (A)
R2NH(CH2)nNH2 (B)
(R1は炭素数9〜29の炭化水素基、R2は炭素数10〜30
の炭化水素基であり、R1、R2の少なくとも一つは飽和
の炭化水素基であり、nは2〜6である。) 本発明の
汚れ防止剤の原料である式(A)の化合物は、R1が炭
素数9〜29の炭化水素基である脂肪酸で、R1は直鎖ま
たは分枝鎖の飽和または不飽和の炭化水素基である。式
(A)の化合物としては、たとえばデカン酸、ラウリン
酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラ
キジン酸、ベヘン酸、リグノセリン酸、セロチン酸、モ
ンタン酸、メリシン酸、オレイン酸、エルカ酸などがあ
り、また、これらを含有する牛脂脂肪酸、硬化牛脂脂肪
酸、パーム油脂肪酸、硬化パーム油脂肪酸、硬化菜種油
脂肪酸、ヤシ油脂肪酸、硬化魚油脂肪酸、さらにイソミ
リスチン酸イソパルミチン酸、イソステアリン酸、イソ
アラキン酸、イソヘキサコサン酸などの合成脂肪酸があ
る。
【0007】式(B)の化合物は、R2が炭素数10〜30
の炭化水素基、nが2〜6のアルキルアルキレンジアミ
ンである。式(B)の化合物としては、たとえばドデシ
ルエチレンジアミン、テトラデシルプロピレンジアミ
ン、ヘキサデシルブチレンジアミン、オクタデシルエチ
レンジアミン、エイコシルヘキセンジアミン、ドコシル
プロピレンジアミン、牛脂アルキルプロピレンジアミ
ン、硬化菜種油アルキルプロピレンジアミン、オレイル
プロピレンジアミンなどがある。式(A)の化合物と式
(B)の化合物とをモル比2/1〜4/5で使用し、た
とえば 150〜230 ℃で反応生成水を留去しながら反応さ
せると、本発明の汚れ防止剤が得られる。また、式
(A)のR1、式(B)のR2の少なくとも一つは飽和の
炭化水素基である。
【0008】上述の限定条件の範囲外では、いずれも十
分な汚れ防止効果が得られない。本発明の石油精製用汚
れ防止剤を用いて汚れを防止するには、たとえば、よご
れ防止剤を有機溶剤で希釈して、取り扱いやすい粘度と
し、連続的に有効分で5〜500ppmを注入するのが好まし
い。注入量が少ないと汚れ防止効果が発揮されず、逆に
多過ぎても効果の向上はなく、経済性が悪くなる。より
好ましい注入量は10〜100ppmである。原油の常圧蒸留工
程を例にとると、注入場所は原油側、残油側の何れでも
よいが、原油側に添加する場合には脱塩槽出口で注入す
るのが好ましく、残油側に添加する場合には蒸留塔残油
出口ポンプのサクション側に注入するのが好ましい。
【0009】
【発明の効果】本発明の石油精製用汚れ防止剤は、熱交
換器内表面あるいはフィルターなどの石油精製装置への
汚れ物質の付着を効果的に防止する。よって、石油精製
工業の各種処理工程において、原油、軽質ナフサ、重質
ナフサ、灯油、軽油、減圧軽油、減圧残油、脱硫残油、
分解残油等に添加することにより、沈着及び堆積する付
着物の量を著しく低減することができる。
【0010】特に、常圧残油を原料とする水素化脱硫装
置や接触分解装置からの残油に添加すると、熱交換器の
汚れやフィルターの閉塞が著しく低減され、汚れ付着物
の除去作業の頻度を少なくすることができると共に、装
置運転条件の苛酷度を上げる事が可能となる。本発明の
汚れ防止剤を添加して精製された重油は、燃焼機器に使
用される際の熱交換器やパイプの汚れをも低減し得る。
【0011】
【実施例】次に実施例により本発明を具体的に説明す
る。
〔汚れ防止試験〕汚れ防止剤の評価は、ASTM(D16
61−64)のNBTL試験を用い、下記の点を変更して行
った。
【0012】ヒーター部の温度を 180℃から 320℃に、
流路の冷却管をガラス製から鉄製に変更した。試料油に
表1に示す汚れ防止剤を所定量添加し、80℃で加熱溶解
し、試験を行ったのち、室温に冷却して冷却管、ヒータ
ー部の保護管をトルエンで洗浄し、布で拭いて、外観を
観察して下記の基準により評価した。
【0013】〇:ほとんど変化なし。
△:茶〜黒色に少し着色している。
×:茶〜黒色に着色し、またはタール状の付着物があ
る。
試験に用いた試料油は脱硫残油であり、その性状は次の
通りである。
密度(g/cm3) 0.9103 (JIS K-2249)
引火点(℃) 9.8 (JIS K-2265)
硫黄分(wt%) 0.18 (JIS K-2541)
動粘度(cSt/50℃) 98.3 (JIS K-2283)
ドライスラッジ(wt%) 0.49 (SMS 742)
結果を表2に示す。
【0014】
【表1】
(注1)「エマゾール871 」Emery Ind.
(注2)イソパルミチン酸 日産化学工業
(注3)「HA18GT」三菱化成工業
(注4)イソステアリン酸 日産化学工業
(注5)重量平均分子量900
【0015】
【表2】
【0016】本発明の汚れ防止剤は、冷却管、保護管に
付着物を与えず、変化がなく、また低添加量でも汚れ防
止効果を発揮した。比較例の汚れ防止剤は、冷却管、保
護管に着色またはタール状の付着物を与えた。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent for petroleum refining for preventing the adhesion of dirt on a petroleum refining apparatus. [0002] In the petroleum refining industry, refinement facilities have recently been advanced from the viewpoint of responding to environmental problems and increasing the production of white oil. The introduction of crackers, hydrodesulfurizers, catalytic crackers, and the like, or the severer operating conditions of these devices, are being promoted. Introduction of these devices or severer operating conditions results in the formation of sludge in residual oil obtained from these devices, causing problems such as fouling of heat exchangers and clogging of filters. When such a failure occurs, the operation of the apparatus is stopped and the operation of removing the contaminants is performed, but frequent operation of this operation leads to the stop of the plant. In order to avoid such a situation, the operating conditions are reduced or the devices are parallelized. However, these are very disadvantageous economically. [0003] In order to prevent the adherence of fouling substances, there have hitherto been proposed many methods of adding a fouling inhibitor to a feedstock. Examples of such an antifouling agent include an amide condensation product of a high molecular weight (molecular weight of 600 to 3000) monocarboxylic acid and an alkylene polyamine (Japanese Patent Publication No. 46-23504), ammonia (Japanese Patent Application Laid-Open No. 54-69106). , Polyalkyleneamine (JP-A-55-129490), polyoxyalkylene carbamate (JP-A-59-232170)
and so on. However, by adding these compounds to feedstocks such as crude oil, it is possible to prevent contamination to some extent, but it is still not enough. SUMMARY OF THE INVENTION An object of the present invention is to provide a high-performance antifouling agent for preventing the adhering of dirt on a heat exchanger and various processing apparatuses in a petroleum refining process. It is. Means for Solving the Problems As a result of intensive studies, the present inventors have found that an amide compound of alkylalkylenediamine is effective as an antifouling agent, and completed the present invention. That is, the present invention provides a compound represented by the following formula (A) and a compound represented by the formula (B) having a molar ratio of 2
/ 1/4/4 reaction alkylene alkylene
An antifouling agent for petroleum refining containing an amide compound of a diamine as an active ingredient . R 1 COOH (A) R 2 NH (CH 2 ) n NH 2 (B) (R 1 is a hydrocarbon group having 9 to 29 carbon atoms, R 2 is a hydrocarbon group having 10 to 30 carbon atoms)
Wherein at least one of R 1 and R 2 is a saturated hydrocarbon group, and n is 2 to 6. The compound of the formula (A) which is a raw material of the antifouling agent of the present invention is a fatty acid wherein R 1 is a hydrocarbon group having 9 to 29 carbon atoms, and R 1 is a linear or branched saturated or unsaturated. Is a hydrocarbon group. Examples of the compound of the formula (A) include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melicic acid, oleic acid, and erucic acid. Yes, and also contain tallow fatty acid, hardened tallow fatty acid, hardened palm oil fatty acid, hardened palm oil fatty acid, hardened rapeseed oil fatty acid, coconut oil fatty acid, hardened fish oil fatty acid, further isomyristate isopalmitic acid, isostearic acid, isoarachinic acid, There are synthetic fatty acids such as isohexacosanoic acid. In the compound of the formula (B), R 2 has 10 to 30 carbon atoms.
And n is an alkylalkylenediamine of 2 to 6. Examples of the compound of the formula (B) include dodecylethylenediamine, tetradecylpropylenediamine, hexadecylbutylenediamine, octadecylethylenediamine, eicosylhexenediamine, docosylpropylenediamine, tallowalkylpropylenediamine, hydrogenated rapeseed oil alkylpropylenediamine, oleylpropylenediamine and so on. When the compound of the formula (A) and the compound of the formula (B) are used in a molar ratio of 2/1 to 4/5 and reacted at, for example, 150 to 230 ° C. while distilling off the reaction water, the dirt of the present invention can be obtained. An inhibitor is obtained. Further, R 1 of formula (A), at least one of R 2 of formula (B) is a saturated hydrocarbon group. [0008] Outside the range of the above-mentioned limiting conditions, no sufficient stain prevention effect can be obtained. To prevent fouling using the petroleum refining antifouling agent of the present invention, for example, diluting the antifouling agent with an organic solvent to obtain a viscosity that is easy to handle, and continuously injecting 5 to 500 ppm of an effective component. Is preferred. If the injection amount is small, the effect of preventing contamination is not exhibited, and if it is too large, the effect is not improved, and the economical efficiency is deteriorated. A more preferable injection amount is 10 to 100 ppm. Taking the atmospheric distillation step of crude oil as an example, the injection location may be either on the crude oil side or on the residual oil side, but when adding to the crude oil side, it is preferable to inject at the outlet of the desalting tank, In the case of addition, it is preferable to inject into the suction side of the distillation column residual oil outlet pump. The antifouling agent for petroleum refining of the present invention effectively prevents the adhering of contaminants to the petroleum refining equipment such as the inner surface of a heat exchanger or a filter. Therefore, in various processing steps of the petroleum refining industry, crude oil, light naphtha, heavy naphtha, kerosene, gas oil, vacuum gas oil, vacuum residue, desulfurization residue,
By adding it to cracked residual oil or the like, the amount of deposits and deposits deposited can be significantly reduced. [0010] In particular, when added to the residual oil from a hydrodesulfurization unit or a catalytic cracking unit using atmospheric residual oil as a raw material, dirt in a heat exchanger and clogging of a filter are remarkably reduced. The frequency can be reduced, and the severity of the operating conditions of the device can be increased. The heavy oil purified by adding the antifouling agent of the present invention can also reduce dirt on heat exchangers and pipes when used in combustion equipment. Next, the present invention will be described in detail with reference to examples. [Stain Prevention Test] Evaluation of the stain preventive agent was performed according to ASTM (D16
61-64), with the following changes. The temperature of the heater section is changed from 180 ° C. to 320 ° C.
The cooling pipe of the channel was changed from glass to iron. A predetermined amount of the stain preventive agent shown in Table 1 was added to the sample oil, heated and dissolved at 80 ° C., tested, cooled to room temperature, and the cooling tube and the protective tube of the heater were washed with toluene, and then washed with a cloth. After wiping, the appearance was observed and evaluated according to the following criteria. Δ: Almost no change. Δ: Brown-black is slightly colored. ×: Brown to black, or tar-like deposits. The sample oil used in the test was desulfurized residual oil, and its properties are as follows. Density (g / cm 3 ) 0.9103 (JIS K-2249) Flash point (℃) 9.8 (JIS K-2265) Sulfur content (wt%) 0.18 (JIS K-2541) Kinematic viscosity (cSt / 50 ℃) 98.3 (JIS K-2283) Dry sludge (wt%) 0.49 (SMS 742) The results are shown in Table 2. [Table 1] (Note 1) “Emazol 871” Emery Ind. (Note 2) Isopalmitic acid Nissan Chemical Industries (Note 3) “HA18GT” Mitsubishi Kasei Kogyo (Note 4) Isostearic acid Nissan Chemical Industries (Note 5) Weight average molecular weight 900 [Table 2] The antifouling agent of the present invention did not give any deposits to the cooling tube and the protective tube, did not change, and exhibited an antifouling effect even at a low addition amount. The antifouling agent of the comparative example provided colored or tar-like deposits on the cooling tube and the protective tube.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C10L 1/22 C10G 7/00 F28F 19/00 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C10L 1/22 C10G 7/00 F28F 19/00
Claims (1)
で表される化合物とのモル比2/1〜4/5での反応生
成物であるアルキルアルキレンジアミンのアミド化合物
を有効成分とする石油精製用汚れ防止剤。 R1COOH (A) R2NH(CH2)nNH2 (B) (R1は炭素数9〜29の炭化水素基、R2は炭素数10〜30の
炭化水素基であり、R1、R2の少なくとも一つは飽和の炭
化水素基であり、nは2〜6である。)(57) [Claims] (1) A compound represented by the following formula (A) and a compound represented by the formula (B):
Amide compound of alkyl alkylenediamine which is a reaction product with a compound represented by the formula (1) at a molar ratio of 2/1 to 4/5
An antifouling agent for petroleum refining, comprising as an active ingredient . R 1 COOH (A) R 2 NH (CH 2 ) n NH 2 (B) (R 1 is a hydrocarbon group having 9 to 29 carbon atoms, R 2 is a hydrocarbon group having 10 to 30 carbon atoms, and R 1 , at least one of R 2 is a saturated hydrocarbon group, n represents 2 to 6.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21067392A JP3381273B2 (en) | 1992-07-16 | 1992-07-16 | Antifouling agent for petroleum refining |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21067392A JP3381273B2 (en) | 1992-07-16 | 1992-07-16 | Antifouling agent for petroleum refining |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0633077A JPH0633077A (en) | 1994-02-08 |
JP3381273B2 true JP3381273B2 (en) | 2003-02-24 |
Family
ID=16593220
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21067392A Expired - Lifetime JP3381273B2 (en) | 1992-07-16 | 1992-07-16 | Antifouling agent for petroleum refining |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3381273B2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4327617B2 (en) | 2004-01-29 | 2009-09-09 | ヤマハ発動機株式会社 | Steering control method for ship propulsion device |
JP4303150B2 (en) | 2004-03-09 | 2009-07-29 | ヤマハ発動機株式会社 | Ship steering device |
JP4327637B2 (en) | 2004-03-26 | 2009-09-09 | ヤマハ発動機株式会社 | Outboard motor steering device and outboard motor |
JP2006001432A (en) | 2004-06-18 | 2006-01-05 | Yamaha Marine Co Ltd | Steering device for small sized vessel |
JP4938271B2 (en) | 2005-09-02 | 2012-05-23 | ヤマハ発動機株式会社 | Ship steering method and steering apparatus |
JP2006224695A (en) | 2005-02-15 | 2006-08-31 | Yamaha Marine Co Ltd | Rudder turning device for vessel |
JP4703263B2 (en) | 2005-03-18 | 2011-06-15 | ヤマハ発動機株式会社 | Ship steering device |
JP2007050823A (en) | 2005-08-19 | 2007-03-01 | Yamaha Marine Co Ltd | Behavior control device for small vessel |
JP4658742B2 (en) | 2005-09-02 | 2011-03-23 | ヤマハ発動機株式会社 | Small ship steering device |
JP4673187B2 (en) | 2005-10-25 | 2011-04-20 | ヤマハ発動機株式会社 | Multi-machine propulsion unit controller |
JP4732860B2 (en) | 2005-11-04 | 2011-07-27 | ヤマハ発動機株式会社 | Electric steering system for outboard motor |
JP5132132B2 (en) | 2006-11-17 | 2013-01-30 | ヤマハ発動機株式会社 | Ship steering device and ship |
JP4884177B2 (en) | 2006-11-17 | 2012-02-29 | ヤマハ発動機株式会社 | Ship steering device and ship |
-
1992
- 1992-07-16 JP JP21067392A patent/JP3381273B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0633077A (en) | 1994-02-08 |
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