JPH0527678B2 - - Google Patents
Info
- Publication number
- JPH0527678B2 JPH0527678B2 JP60001428A JP142885A JPH0527678B2 JP H0527678 B2 JPH0527678 B2 JP H0527678B2 JP 60001428 A JP60001428 A JP 60001428A JP 142885 A JP142885 A JP 142885A JP H0527678 B2 JPH0527678 B2 JP H0527678B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrocarbon
- feed oil
- added
- coking agent
- 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
Ａ 産業上の利用分野
本発明は、炭化水素類を650℃未満の処理温度
で処理して石油、石油化学製品及び／または中間
製品を製造する炭化水素処理プロセス構成機器の
コーキングを防止する方法、更に詳しく述べれば
炭化水素類を650℃未満の温度で精製、分離、抽
出、脱硫、改質、重合、熱分解、接触分解、合成
反応またはそれらの二種以上の組合わせプロセス
等によつて処理して石油、石油化学製品および／
またはそれらの中間製品を製造する熱交換器、加
熱炉、反応塔それらの連結配管等を含むプロセス
の構成機器にコーキング防止剤を供給して、コー
キングを防止する方法に関する。
Ｂ 従来の技術
石油・石油化学工程の多くの炭化水素類処理プ
ロセスにおいては、プロセスに入る前の熱交換
器、加熱炉及び該プロセスの反応塔等で、炭化水
素フイード油を高温に加熱し、処理の目的を達し
ている。この時、処理プロセス構成機器内の特に
高温部でコークス状物（コークス状のフアウリン
グ）が厚く堆積し、伝熱を悪くしたり、ストリー
ムの流れを悪くするなど、種々の弊害をもたらす
ことが知られている。この弊害を取除くために、
該プラントの運転担当者は、デコーキング或はク
リーニングの頻度を上げて、対処しているのが一
般的である。これは省エネルギー、工程合理化と
いつた面からみれば、極めて好ましくない。
ここでいう炭化水素類処理プロセスの例として
は、原油常圧蒸留塔、減圧蒸留塔、水素化脱硫
塔、ビスブレーカー、コーカー、芳香族炭化水素
類抽出塔などが挙げられる。これらのプロセス
は、比較的重合・コーキングの起こし易い炭化水
素油をフイードしている事、更に比較的温度の高
い条件で運転している事等により、コーキング問
題は大きく顕在化して、その対策がのぞまれてい
る。
コーキングの原因は、基本的にはフイード油中
の重質分、或はフイード油中で部分的に重合して
出来た重質分がプロセス構成機器の器壁上に付着
し、これが更に高温度に長時間さらされてコーク
ス状にまで成長することにある。このコークス状
物の生成及び堆積を抑える方法としては、例えば
USP4444649にみるように、リン酸誘導体を添加
する方法などが提案されている。しかし、従来報
告されている方法のどれをとつても、充分満足の
いくレベルにほど遠く、より一層の改善が望まれ
ていた。
Ｃ 発明が解決しようとする問題点
そこで、本発明は上記問題点を解消することを
目的とするものである。すなわち、高温において
もコーキング防止作用があり、安定性があり、炭
化水素に可溶で取扱いが容易であり、広汎な炭化
水素処理プロセスに適するプロセス構成機器用の
すぐれたコーキング防止剤によつてプロセス構成
機器のコーキングを防止する方法を提供すること
を目的とする。
Ｄ 問題点を解決するための手段
本発明者らは、かような炭化水素類処理プロセ
スの熱交換器、加熱炉、反応塔等で発生するコー
キングについて、その抑制方法を鋭意検討した結
果本発明に到達したものである。
本発明によれば、下記の一般式及び／或は式
で示される化合物
（ここで、R1、R2、R3、R4、R5、R6、R7、R8
は夫々独立に水素原子或は炭素数１〜30のアルキ
ル基、シクロアルキル基、アリール基、アリカノ
ール基、アラルキル基、若しくはアルケニル基で
あり、夫々同一或は異種のものでもよく、又、ｘ
は１〜６の整数である）を、該プロセスのフイー
ド油中に10〜5000ppm、望むらくは、10〜
1000ppm添加することにより、熱交換器、加熱
炉、反応塔等で発生するコーキングを抑えられる
利点がある。本発明では、式及び／或は式で
示される化合物をフイード油に対して10〜
5000ppm、望むらくは10〜1000ppm添加するとし
ているがこれはあまり少量では充分な効果が期待
出来ない事、又、5000ppm以上では効果は充分あ
るものの経済的にみて限界あるとの判断によるも
のである。又、本発明では、式及び／或は式
で示される少なくとも一種の化合物の使用を提案
しているがこれら化合物の二種以上混合して使用
する事或は同時に他種類のフアウリング防止剤或
はコーキング防止剤と併用することも出来、本発
明はそのような組み合わせに対し、何等制限を与
えるものではない。本発明で述べる式、式で
示される化合物の実際の例としては、N.N−ジ
エチルチオウレア、N.N−ジブチルチオウレア、
テトラメチルチウラムモノスルフイルド、テトラ
ブチルウラムモノスルフイド、テトラエチルチウ
ラムジスルフイド、テトラブチルチウラムジスル
フイドなどが挙げられる。
本発明を工業的に実施するにあたつては、式
及び／或は式に示された化合物を炭化水素系溶
剤、含酸素炭化水素系溶剤含等有機溶剤に溶解せ
しめ、フイード油中に注入するのが最も一般的な
方法である。又、薬品がフイード油中に添加され
てから、対象とする熱交換器、加熱炉、反応塔に
到達する迄の間に、薬品が均一にフイード油中に
混ざり合うように注入点と問題個所の間をできる
だけ長くとり、且つ途中に屈曲点を設けたりする
ことは、成功する上で必要なことである。
次に本発明の方法を実施例によつて具体的に説
明する。しかし、本発明は以下の実施例に何等制
限されるものではない。
Ｅ 実施例
450℃に加熱したテストチユーブ（材質：
SUS316、内径2.2mm、長さ400mm）に、燈油90％
＋トルエン10％の混合物を一定量ずつフイードし
た。所定時間経過した後、テストチユーブをとり
だし、テスト前後のチユーブ重量比から付着コー
クス量を算出した。
A. Industrial Application Field The present invention relates to a method for preventing coking of hydrocarbon processing process components for producing petroleum, petrochemical products and/or intermediate products by processing hydrocarbons at processing temperatures below 650°C; More specifically, hydrocarbons are treated at temperatures below 650°C by purification, separation, extraction, desulfurization, reforming, polymerization, thermal cracking, catalytic cracking, synthetic reaction, or a combination process of two or more of these. petroleum, petrochemicals and/or
The present invention also relates to a method of preventing coking by supplying an anti-coking agent to the constituent equipment of a process that produces intermediate products thereof, including heat exchangers, heating furnaces, reaction towers, and connecting piping between these. B. Prior Art In many hydrocarbon treatment processes in petroleum and petrochemical processes, hydrocarbon feed oil is heated to a high temperature in a heat exchanger, heating furnace, reaction tower, etc. before entering the process. The purpose of processing has been achieved. At this time, it is known that coke-like substances (coke-like fouling) accumulate thickly in particularly high-temperature parts of the treatment process components, causing various problems such as impairing heat transfer and stream flow. It is being In order to eliminate this negative effect,
Generally, those in charge of operating the plant deal with the problem by increasing the frequency of decoking or cleaning. This is extremely undesirable from the standpoint of energy conservation and process rationalization. Examples of the hydrocarbons treatment process mentioned here include a crude oil normal pressure distillation column, a vacuum distillation column, a hydrodesulfurization column, a vis breaker, a coker, an aromatic hydrocarbons extraction column, and the like. Because these processes feed hydrocarbon oils that are relatively prone to polymerization and coking, and are operated at relatively high temperatures, the coking problem has become more apparent, and no countermeasures have been taken. It is desired. The cause of coking is basically that heavy components in the feed oil, or heavy components formed by partial polymerization in the feed oil, adhere to the walls of process components, and this is caused by higher temperatures. The reason is that when exposed to water for a long time, it grows to a coke-like consistency. As a method of suppressing the generation and accumulation of this coke-like material, for example,
As seen in USP4444649, methods of adding phosphoric acid derivatives have been proposed. However, all of the methods reported so far are far from fully satisfactory, and further improvements have been desired. C Problems to be Solved by the Invention Therefore, the present invention aims to solve the above problems. In other words, it has anti-coking properties even at high temperatures, is stable, soluble in hydrocarbons, easy to handle, and is suitable for a wide range of hydrocarbon processing processes. It is an object of the present invention to provide a method for preventing caulking of component equipment. D. Means for Solving the Problems The present inventors have intensively studied methods for suppressing coking that occurs in heat exchangers, heating furnaces, reaction towers, etc. in hydrocarbon treatment processes, and have developed the present invention. has been reached. According to the present invention, a compound represented by the following general formula and/or formula (Here, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8
are each independently a hydrogen atom or an alkyl group, cycloalkyl group, aryl group, arykanol group, aralkyl group, or alkenyl group having 1 to 30 carbon atoms, and may be the same or different, and x
is an integer from 1 to 6) in the feed oil of the process at 10 to 5000 ppm, preferably 10 to 5000 ppm, preferably 10 to
Adding 1000 ppm has the advantage of suppressing coking that occurs in heat exchangers, heating furnaces, reaction towers, etc. In the present invention, the compound represented by the formula and/or formula is added to the feed oil in an amount of 10 to
It is said that 5000ppm, preferably 10 to 1000ppm, should be added, but this is based on the judgment that sufficient effects cannot be expected with very small amounts, and that there is a limit from an economical point of view if more than 5000ppm is effective. . In addition, the present invention proposes the use of at least one compound represented by the formula and/or formula, but it is also possible to use a mixture of two or more of these compounds or to simultaneously use other types of anti-fouling agents or It can also be used in combination with a coking inhibitor, and the present invention does not impose any restrictions on such combinations. Actual examples of the formulas and compounds represented by the formulas described in the present invention include NN-diethylthiourea, NN-dibutylthiourea,
Examples include tetramethylthiuram monosulfide, tetrabutylthiuram monosulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide. In carrying out the present invention industrially, the compound represented by the formula and/or the formula is dissolved in an organic solvent such as a hydrocarbon solvent, an oxygenated hydrocarbon solvent, etc., and the solution is injected into feed oil. This is the most common method. In addition, from the time the chemicals are added to the feed oil until they reach the target heat exchanger, heating furnace, and reaction tower, injection points and problem areas are checked so that the chemicals are evenly mixed into the feed oil. Making the gap as long as possible and providing bending points along the way are necessary for success. Next, the method of the present invention will be specifically explained using examples. However, the present invention is not limited to the following examples in any way. E Example Test tube heated to 450℃ (Material:
SUS316, inner diameter 2.2mm, length 400mm), kerosene 90%
A mixture of +10% toluene was fed in fixed amounts. After a predetermined period of time had elapsed, the test tube was taken out, and the amount of adhering coke was calculated from the weight ratio of the tube before and after the test.
【表】
Ｆ 発明の効果
本発明の方法によれば、炭化水素処理プロセス
構成機器のコーキングは著しく抑制され、熱伝
達、熱効率の低下と流体輸送の阻害が軽減される
のみならず、頻繁な運転停止とクリーニングが緩
和され、省力、省エネルギー、生産合理化及び設
備保全に奏する効果は大きい。[Table] F Effects of the Invention According to the method of the present invention, coking of hydrocarbon treatment process components is significantly suppressed, and not only is the reduction in heat transfer, thermal efficiency and inhibition of fluid transport reduced, but also the frequent operation is reduced. Stoppages and cleaning are alleviated, which has great effects on labor saving, energy saving, production rationalization, and equipment maintenance.
Claims (1)
て石油、石油化学製品および／または中間製品を
製造する炭化水素処理プロセスの構成機器に下記
の一般式 （ここで、R1、R2、R3、R4、R5、R6、R7、
R8は夫々独立に水素原子或は炭素数１〜30のア
ルキル基、シクロアルキル基、アリール基、アル
カノール基、アラルキル基、若しくはアルケニル
基であり、夫々同一或は異種のものでも良く、
又、ｘは１〜６の整数である）で示す化合物から
なる群から選ばれる少なくとも一種の化合物を有
効成分として含有するコーキング防止剤を供給す
ることを特徴とする当該炭化水素処理プロセス構
成機器のコーキングを抑制する方法。 ２ 炭化水素処理プロセスが炭化水素数の精製、
分離、抽出、脱硫、改質、重合、熱分解、接触分
解、合成反応またはそれらの二重以上の組合わせ
プロセスである特許請求の範囲第１項に記載の方
法。 ３ 前記コーキング防止剤を予め炭化水素フイー
ド油中に混合添加する特許請求の範囲第１項に記
載の方法。 ４ 前記コーキング防止剤を予め有機溶剤中に溶
解せしめたのち炭化水素フイード油中に注入添加
する特許請求の範囲第３項に記載の方法。 ５ 前記コーキング防止剤を炭化水素フイード油
中に注入するに際し、炭化水素フイード油に対し
10〜5000ppmの範囲に相当する量で添加する特許
請求の範囲第３項ないし第４項に記載の方法。[Claims] 1. The following general formula is applied to the components of a hydrocarbon processing process that processes hydrocarbons at a processing temperature of less than 650°C to produce petroleum, petrochemical products, and/or intermediate products. (Here, R1, R2, R3, R4, R5, R6, R7,
R8 is each independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group, an aryl group, an alkanol group, an aralkyl group, or an alkenyl group, and each of them may be the same or different;
Further, the hydrocarbon treatment process component equipment is characterized in that it supplies an anti-coking agent containing as an active ingredient at least one compound selected from the group consisting of compounds represented by (x is an integer from 1 to 6). How to suppress caulking. 2 The hydrocarbon processing process involves refining a number of hydrocarbons,
The method according to claim 1, which is a process of separation, extraction, desulfurization, modification, polymerization, thermal cracking, catalytic cracking, synthetic reaction, or a combination of two or more thereof. 3. The method according to claim 1, wherein the anti-coking agent is mixed and added to the hydrocarbon feed oil in advance. 4. The method according to claim 3, wherein the anti-coking agent is dissolved in an organic solvent in advance and then added by injection into the hydrocarbon feed oil. 5 When injecting the anti-coking agent into the hydrocarbon feed oil,
5. The method according to claim 3, wherein the amount of the additive is added in an amount corresponding to a range of 10 to 5000 ppm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP142885A JPS61162589A (en) | 1985-01-10 | 1985-01-10 | Prevention of coking in hydrocarbon-treating process |
| US06/764,879 US4636297A (en) | 1984-08-16 | 1985-08-12 | Method for preventing coking in hydrocarbon treatment process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP142885A JPS61162589A (en) | 1985-01-10 | 1985-01-10 | Prevention of coking in hydrocarbon-treating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61162589A JPS61162589A (en) | 1986-07-23 |
| JPH0527678B2 true JPH0527678B2 (en) | 1993-04-21 |
Family
ID=11501182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP142885A Granted JPS61162589A (en) | 1984-08-16 | 1985-01-10 | Prevention of coking in hydrocarbon-treating process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61162589A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1309810C (en) * | 2005-07-26 | 2007-04-11 | 张喜文 | Coke inhibitor of high-temperature refining equipment |
| RU2505584C2 (en) * | 2009-03-04 | 2014-01-27 | Юоп Ллк | Method for prevention of coke formation catalysed by metal |
| CN114479949B (en) * | 2022-02-18 | 2023-03-03 | 河南科技大学 | A two-stage waste plastic pyrolysis device and pyrolysis system |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147792A (en) * | 1984-08-16 | 1986-03-08 | Hakutou Kagaku Kk | Method of preventing caulking of cracking furnace for ethylene |
-
1985
- 1985-01-10 JP JP142885A patent/JPS61162589A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61162589A (en) | 1986-07-23 |
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