JPS6147792A - Method of preventing caulking of cracking furnace for ethylene - Google Patents
Method of preventing caulking of cracking furnace for ethyleneInfo
- Publication number
- JPS6147792A JPS6147792A JP16994184A JP16994184A JPS6147792A JP S6147792 A JPS6147792 A JP S6147792A JP 16994184 A JP16994184 A JP 16994184A JP 16994184 A JP16994184 A JP 16994184A JP S6147792 A JPS6147792 A JP S6147792A
- Authority
- JP
- Japan
- Prior art keywords
- group
- ethylene
- cracking furnace
- coking
- petroleum
- 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.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、エチレン分解炉の分解チューブ及び/或は分
解炉出口にある冷却用熱交換器(TLE)におけるコー
キングを防止する方法、更に詳しくは、石油系原料を分
解してエチレンを製造するためのエチレン分解炉にコー
キング防止剤を供給することにより分解チューブ及び/
或は後続の冷却用熱交換器におけるコーキングを防止す
る方法1こ関する。エチレン製造装置では、エタン、プ
ロパン等、のガス状炭化水素或はナフサ、軽油等の液状
炭化水素をフィード油とし、これを1000℃近くに加
熱された熱分解炉に送り込んで熱分解せしめ、エチシン
。プロピレンを製造している。この熱分解炉における問
題点の1つに、分解チューブ及び/或は後続のTLE発
生するコークス付着・堆積がある。これらの個所でコー
クス応(堆積すると、熱伝導が悪くなり、エネルギーの
ロスとなるのみでなく、チューブ内圧力が上昇し、運転
の継続不可能、危険を招くことになる。そこで、当該プ
ラント担当者は、一定期間毎に、或は緊急に運転を停止
し、機械的に或は蒸気や空気の導入によって付着・堆積
物の除去(デコーキング)を行い対処している。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for preventing coking in a cracking tube of an ethylene cracking furnace and/or a cooling heat exchanger (TLE) at the outlet of the cracking furnace, and more specifically, a method for preventing coking in a cracking tube of an ethylene cracking furnace and/or a cooling heat exchanger (TLE) at the exit of the cracking furnace. By supplying an anti-coking agent to an ethylene cracking furnace for producing ethylene,
Alternatively, the present invention relates to a method for preventing coking in a subsequent cooling heat exchanger. In ethylene production equipment, gaseous hydrocarbons such as ethane and propane, or liquid hydrocarbons such as naphtha and light oil are used as feed oil, and this is fed into a pyrolysis furnace heated to nearly 1000°C to be thermally decomposed to produce ethyl ethylene. . Manufactures propylene. One of the problems with this pyrolysis furnace is the adhesion and deposition of coke generated in the cracking tube and/or subsequent TLE. If coke reaction (accumulation) occurs in these locations, heat conduction will be poor and energy will be lost, and the pressure inside the tube will increase, making it impossible to continue operation and causing danger. To cope with this problem, operators stop operation at regular intervals or in an emergency, and remove adhesion and deposits (decoking) mechanically or by introducing steam or air.
この好ましからざるコーキングの原因は、基本的にはフ
ィード油の或は分解油の部分的重合、そしてその後に続
く脱水素反応である。コーキング反応の速度に関係する
因子は、フィード油の種類(組成)、分解炉の構造、運
転条件などである。しかし、経済的な面から、或は運転
上の必要性から、これら因子を変え、コーキングを押さ
えようとする試みは、自ら限界がある。従って、これら
コークスの堆積を除くために、強制的デコーキングの頻
度を上げていく方法が専らとられている。一方、化学的
にコーキングを抑えようとする試みもあり、硫化水素、
ジメチルジスルフィド(DMDS)などイオウ化合物が
使われた例はある。又、リン酸、亜リン酸誘導体の如き
リン化合物がコーキング抑制に効果ありとする報告もあ
る(特開昭54−108808)。The cause of this undesirable coking is essentially the partial polymerization of the feed oil or of the cracked oil and the subsequent dehydrogenation reaction. Factors related to the rate of coking reaction include the type (composition) of feed oil, the structure of the cracking furnace, and operating conditions. However, attempts to suppress coking by changing these factors from an economic standpoint or operational necessity have their own limits. Therefore, in order to remove these coke deposits, the method of increasing the frequency of forced decoking is exclusively used. On the other hand, there are attempts to chemically suppress coking, such as hydrogen sulfide,
There are examples of sulfur compounds such as dimethyl disulfide (DMDS) being used. There is also a report that phosphorus compounds such as phosphoric acid and phosphorous acid derivatives are effective in suppressing coking (Japanese Patent Application Laid-Open No. 108808/1983).
しかし、硫化水素、DMDSは取り扱いが極めて面倒な
上に、経済的に満足のいく程効果は上がっていない。一
方、リン化合物は本発明者らの研究によれば、反対にコ
ーキングを促進する事もあり、実際の使用はかなり限定
される。又イオウ化合物、リン化合物の多くは、炭化水
素に不溶のものが多く、実際に適用する上で難しいもの
が多い。いずれにせよ、取り扱い上、或はその効果の上
で充分満足のいく薬品は現在見出だされていない。本発
明者らは、かかるエチレン分解炉分解チューブ及びTL
Eにおけるコーキング現象を解析し、コーキング抑制効
果のある薬品を種々検討した結果、下記の一般式■及び
■で示されるイオウ化合物が、その効果において更に取
り扱いにおいて極めて有利である事を見出だし、′本発
明に到達したものである。However, hydrogen sulfide and DMDS are extremely troublesome to handle and are not economically satisfactory. On the other hand, according to research conducted by the present inventors, phosphorus compounds may actually promote coking, so their actual use is quite limited. Furthermore, many of the sulfur compounds and phosphorus compounds are insoluble in hydrocarbons, making them difficult to actually apply. In any case, no drug has yet been found that is fully satisfactory in terms of handling and effectiveness. The present inventors have developed such an ethylene cracking furnace cracking tube and a TL
As a result of analyzing the coking phenomenon in E and examining various chemicals that have a coking inhibiting effect, we discovered that the sulfur compounds represented by the following general formulas (■) and (■) are extremely advantageous in terms of their effects and handling. This has led to the present invention.
S S 5(I)
(If)ここでR1,R2,R
3,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間−或は異種のものでもよく
、又Xは1〜6の整数である。SS5(I)
(If) Here R1, R2, R
3, R4, R5, R6, R7, R8 are 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 may be different types, and X is an integer from 1 to 6.
本発明に述べる式■或は式■で示される化合物の実際の
例としては、NN−ジエチルチオウレア、N、N−ジブ
チルチオウレア、N、N−ジラウリルチオウレア、テト
ラメチルチウラムモノスルフィド、テトラブチルチウラ
ムモノスルフィド、テトラエチルチウラムジスルフィド
、テトラブチルチウラムジスルフィドなどが挙げられる
。Practical examples of compounds represented by formula (1) or formula (2) described in the present invention include NN-diethylthiourea, N,N-dibutylthiourea, N,N-dilaurylthiourea, tetramethylthiuram monosulfide, and tetrabutylthiuram. Examples include monosulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide.
本発明によれば、式I或は式■に示された化合物をエチ
レン分解炉フィード油中に10〜5000pI)III
。According to the present invention, a compound of formula I or formula (III) is added to an ethylene cracking furnace feed oil at a concentration of 10 to 5000 pI)
.
望むらくは50〜loooppmを添加することにより
、エチレン分解炉分解チューブ及び/或はTLEにおけ
るコークス生成を抑えられる利点がある。By preferably adding 50 to 100 ppm, there is an advantage that coke formation in the ethylene cracking furnace cracking tube and/or TLE can be suppressed.
本発明では、式I或は■で示される化合物をフィード油
に対して10〜soooppm、望むらくは50〜11
000pp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こと、また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I或は■
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を混合して用いること、
或は同時に硫化水素DMDSなど既にコーキング防止効
果の知られたイオウ化合物、若しくはリン化合物などと
併用することは何等差支えなく、これにより何ら制限さ
れるものではない。しかも以上の組み合わせによっては
相乗効果も期待できる。In the present invention, the compound represented by formula I or
000ppm is added, but this is because a sufficient effect cannot be expected with a very small amount, and 5000ppm is added.
The above is based on the judgment that although the effects are sufficient, there are limits from an economic standpoint. Moreover, in the present invention, formula I or ■
Although it is proposed to use at least one kind of compound shown in the following, the use of a mixture of two or more of these compounds
Alternatively, there is no problem in using hydrogen sulfide DMDS in combination with a sulfur compound or a phosphorus compound already known to have an anti-coking effect, and there is no limitation thereto. Furthermore, synergistic effects can be expected depending on the combination of the above.
本発明を工業的に実施するにあたっては、式1或船■に
示された化合物を、炭化水素系溶剤、アルコールの如き
含酸素溶剤、ジメチルスルフオキシドの如き含イオウ溶
剤など一般有機溶剤に溶解せしめ、フィード油中に注入
するのが最も一般的な方法である。注入にあたっては薬
品がパルス注入にならないよう連続的にスムースに添加
するようにするのが望ましい。又、薬品がフィード油に
添加されてから、分解炉に至るまでの間に、薬品が出来
るだけ均一にフィード油中に混ざり合うように、゛配管
の途中にバルブを設けたり、スタティックミキサーを設
けたり或は配管に曲す部分を設けたりする工夫をするこ
とは、成功する上で必要なことである。この意味から、
本発明で述べる薬品を、あらかじめフィード油中に添加
しておくのが最も理想的であるが、これが出来ない場合
には、分解炉人1口からフィード油上流側の出来る限り
遠い所に注入点を置くようにするのが望ましい。In order to carry out the present invention industrially, the compound represented by Formula 1 or Ship (2) is dissolved in a general organic solvent such as a hydrocarbon solvent, an oxygen-containing solvent such as alcohol, or a sulfur-containing solvent such as dimethyl sulfoxide. The most common method is to inject it into the feed oil. When injecting, it is desirable to add the chemical continuously and smoothly to avoid pulse injection. In addition, in order to mix the chemicals into the feed oil as uniformly as possible after the chemicals are added to the feed oil until it reaches the cracking furnace, a valve is installed in the middle of the piping or a static mixer is installed. In order to be successful, it is necessary to take measures such as bending or providing bends in the piping. From this meaning,
It is most ideal to add the chemicals described in this invention to the feed oil in advance, but if this is not possible, place the injection point as far as possible upstream of the feed oil from the first port of the cracking furnace. It is desirable to place
次に、本発晩の方法を実施例によって具体的に祥明する
。しかし、本発明は以下の実施例に何ら制限されるもの
ではない。Next, the present method will be explained in detail by way of examples. However, the present invention is not limited to the following examples.
[実施例コ
ロ50℃或は850℃に加熱したテストチューブ(材質
:SOS 316.内径2.2mm、長さ 400mm
)に、ナフサ及び水をそれぞれ一定量ずつフィードした
。所定時間経過してから、テストチューブを取り出し、
テスト前後の重量比から、付着コークス量を算出した。[Example test tube heated to 50°C or 850°C (Material: SOS 316. Inner diameter 2.2mm, length 400mm)
) was fed with fixed amounts of naphtha and water. After the specified time has elapsed, remove the test tube and
The amount of attached coke was calculated from the weight ratio before and after the test.
コーキング抑制のための薬品は、ナフサ中に所定量溶解
し、これを実験に供した。テストは10時間行ったが、
コーキングの激しい場合には途中でチューブが閉塞して
しまったので、そ、の場合にはその時点でテストを中止
し、付着コーキング量を測定した。A predetermined amount of a chemical for suppressing coking was dissolved in naphtha, and this was used in the experiment. The test lasted 10 hours,
If there was heavy caulking, the tube would become blocked midway through, so in that case, the test was stopped at that point and the amount of caulking deposited was measured.
Claims (1)
分解炉に、下記の一般式 ▲数式、化学式、表等があります▼[ I ]▲数式、化
学式、表等があります▼[II] (ここで、R_1、R_2、R_3、R_4、R_5、
R_6、R_7、R_8は夫々独立に水素原子或は炭素
数の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あるいは異種のものでもよく、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
エチレン分解炉の分解チューブ及び/或は後続の冷却用
熱交換器中におけるコークスの生成を抑制する方法。 2、前記コーキング防止剤を予め石油系原料中に混合添
加す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有機溶剤中に溶解せし
めたのち石油系原料中に注入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石油系原料に対して10〜
5000ppmの範囲に相当する量で添加する特許請求
の範囲第2項ないし第3項に記載の方法。[Scope of Patent Claims] 1. The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼[II] (Here, R_1, R_2, R_3, R_4, R_5,
R_6, R_7, and R_8 are 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 may be the same or different, Further, the cracking tube of the ethylene cracking furnace 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 the compounds represented by (X is an integer from 1 to 6) and/or Or a method of suppressing coke formation in a subsequent cooling heat exchanger. 2. The method according to claim 1, wherein the anti-coking agent is mixed and added to the petroleum-based raw material in advance. 3. The method according to claim 1, wherein the anti-coking agent is dissolved in an organic solvent in advance and then injected into the petroleum-based raw material. 4. Add the above anti-coking agent to petroleum-based raw materials from 10 to
The method according to claims 2 to 3, wherein the additive is added in an amount corresponding to a range of 5000 ppm.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16994184A JPS6147792A (en) | 1984-08-16 | 1984-08-16 | Method of preventing caulking of cracking furnace for ethylene |
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 |
---|---|---|---|
JP16994184A JPS6147792A (en) | 1984-08-16 | 1984-08-16 | Method of preventing caulking of cracking furnace for ethylene |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6147792A true JPS6147792A (en) | 1986-03-08 |
JPH0479396B2 JPH0479396B2 (en) | 1992-12-15 |
Family
ID=15895737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16994184A Granted JPS6147792A (en) | 1984-08-16 | 1984-08-16 | Method of preventing caulking of cracking furnace for ethylene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6147792A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61162589A (en) * | 1985-01-10 | 1986-07-23 | Hakutou Kagaku Kk | Prevention of coking in hydrocarbon-treating process |
JP2009127818A (en) * | 2007-11-27 | 2009-06-11 | Showa Corp | Damping force adjusting structure for hydraulic shock absorber |
-
1984
- 1984-08-16 JP JP16994184A patent/JPS6147792A/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61162589A (en) * | 1985-01-10 | 1986-07-23 | Hakutou Kagaku Kk | Prevention of coking in hydrocarbon-treating process |
JPH0527678B2 (en) * | 1985-01-10 | 1993-04-21 | Hakuto Kk | |
JP2009127818A (en) * | 2007-11-27 | 2009-06-11 | Showa Corp | Damping force adjusting structure for hydraulic shock absorber |
Also Published As
Publication number | Publication date |
---|---|
JPH0479396B2 (en) | 1992-12-15 |
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