JPH0519080B2 - - Google Patents
Info
- Publication number
- JPH0519080B2 JPH0519080B2 JP58231219A JP23121983A JPH0519080B2 JP H0519080 B2 JPH0519080 B2 JP H0519080B2 JP 58231219 A JP58231219 A JP 58231219A JP 23121983 A JP23121983 A JP 23121983A JP H0519080 B2 JPH0519080 B2 JP H0519080B2
- Authority
- JP
- Japan
- Prior art keywords
- heat exchanger
- effluent
- tube
- layer
- mixture
- 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
- 239000010410 layer Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005336 cracking Methods 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920002050 silicone resin Polymers 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- 238000013007 heat curing Methods 0.000 claims description 3
- 150000003254 radicals Chemical class 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 238000001723 curing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000011109 contamination Methods 0.000 description 10
- 229910052751 metal Chemical class 0.000 description 9
- 239000002184 metal Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- -1 Methyl -acetyl Chemical group 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/002—Cooling of cracked gases
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
Description
【発明の詳細な説明】
本発明は炭化水素出発物質をアルケンに熱分解
するためのプラントに関するものであり、該プラ
ントは外側から加熱される反応管（コイル）を有
する分解加熱炉と、反応管流出物を冷却するため
に該分解加熱炉に連結した外殻−管式熱交換器
（「クエンチ」クーラー、「トランスフアーライン」
熱交換器、TLX、多管式熱交換器）とを含み、
熱交換器の外殻側で水蒸気を発生させるものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a plant for the pyrolysis of hydrocarbon starting materials to alkenes, the plant comprising a cracking furnace with an externally heated reaction tube (coil); A shell-and-tube heat exchanger ("quench" cooler, "transfer line") connected to the cracking furnace to cool the effluent.
heat exchanger, TLX, shell-and-tube heat exchanger),
Steam is generated on the outer shell side of the heat exchanger.
天然ガスからナフサや軽油にまで及ぶ広範囲の
出発物質からエテンやプロペンのようなアルケン
を製造するのに一般に用いられるこの種の装置
（プラント）は、Kirk−Othmerによる
Encyclopedia of Chemical Technology 第３
版９巻（1980年）400〜408頁、特に403〜408頁に
記載されている。 This type of plant, commonly used to produce alkenes such as ethene and propene from a wide range of starting materials ranging from natural gas to naphtha and gas oil, was developed by Kirk-Othmer.
Encyclopedia of Chemical Technology Part 3
Edition, Volume 9 (1980), pages 400-408, especially pages 403-408.
ここ数年の間に、炭化水素出発物質の種類を問
わずに適合しうる、これらの装置の分解加熱炉用
の多くの一般条件が見いだされ、そして「コンピ
ユーター」によつて制御される制御プログラムま
で設計されるに到つた。このようなプログラム
は、動力収支に関して分解加熱炉の最適操作を保
証し、それによつて分解加熱炉の数ケ月に及ぶ連
続運転も可能となつた。 During the last few years, many general conditions have been found for the cracking furnaces of these devices, which can be adapted to any type of hydrocarbon starting material, and control programs controlled by "computers". It was finally designed. Such a program ensured optimal operation of the cracking furnace in terms of power balance, which also made continuous operation of the cracking furnace possible for several months.
分解加熱炉の反応管流出物は、外殻−管式熱交
換器内において750〜900℃から350〜560℃に冷却
され（前掲のKirk−Othmerの407頁の第５表参
照）、同時に105〜125bara（バール絶対）の圧力
を有する水蒸気を発生する。前記の冷却は、分解
加熱炉からの流出物中で断熱条件下の反応が起き
てアルケンの収率に悪影響が及ぶのを避けるため
に行われる。 The reaction tube effluent of the decomposition furnace is cooled from 750-900°C to 350-560°C in a shell-tube heat exchanger (see Table 5 of Kirk-Othmer, supra, p. 407), and at the same time 105 Generates water vapor with a pressure of ~125bara (bar absolute). Said cooling is carried out in order to avoid reactions occurring under adiabatic conditions in the effluent from the cracking furnace, which would have an adverse effect on the alkene yield.
しかしながら、反応管流出物を冷却するときに
熱交換器の管が汚染され、この汚染は熱伝達率を
低下させるものとなる。同時に高圧水蒸気の発生
に利用される反応管流出物の顕熱が益々低下す
る。一方、外殻−管式熱交換器からの流出物の温
度は益々上昇する。 However, when cooling the reaction tube effluent, the heat exchanger tubes become contaminated, and this contamination reduces the heat transfer coefficient. At the same time, the sensible heat of the reaction tube effluent, which is used to generate high-pressure steam, is increasingly reduced. Meanwhile, the temperature of the effluent from the shell-and-tube heat exchanger increases increasingly.
今日までこの減少は不可避であると考えられて
いた。この現象は、分解加熱炉の流出物から重質
炭化水素成分が低温の熱交換器の表面上に凝縮
し、熱交換器の管壁を支配する温度の下で該凝縮
生成物の脱水素化反応が起き続けるためであると
されていた（1978年５月15日付のLohr.B＆Ｈ
Dittmann、OGJ参照）。 Until now, this decline was considered inevitable. This phenomenon is characterized by the condensation of heavy hydrocarbon components from the effluent of a cracking furnace onto the surface of a cold heat exchanger, and the dehydrogenation of the condensed products under the temperature prevailing on the tube walls of the heat exchanger. (Lohr.B&H, May 15, 1978)
Dittmann, OGJ).
オランダ国特許出願第7007556号明細書による
と、冷却槽内の冷却液中に導入管を介して分解ガ
ス混合物を導入することによつてそれを冷却する
別の冷却システムにおいて、導入管の外側に断熱
材を施すことによつて導入管の内側温度を比較的
高温に保ち、タールや炭素質物質を管の内側に凝
縮しにくくすることにより、導入管の汚染の問
題、さらにはタールや炭素質物質が導入管の内側
に沈積して管を閉塞させる問題をも起きないよう
にしている。この断熱層は数cmの厚さを有する。 According to Dutch patent application no. By applying insulation, the temperature inside the inlet pipe is maintained at a relatively high temperature, making it difficult for tar and carbonaceous substances to condense inside the pipe, thereby reducing the problem of contamination of the inlet pipe and further reducing tar and carbonaceous substances. This also prevents the problem of material depositing inside the inlet tube and clogging the tube. This insulation layer has a thickness of several centimeters.
この解決策は外殻−管式熱交換器には適用でき
ない。なぜならば、外殻−管式熱交換器の管を断
熱性にすることは、反応管流出物の完全冷却を放
棄することになるからである。 This solution is not applicable to shell-and-tube heat exchangers. This is because making the tubes of a shell-and-tube heat exchanger adiabatic means giving up complete cooling of the reaction tube effluent.
もし、汚染の原因となる反応管流出物中の物質
を透過させない不活性な層によつて熱交換器の管
の内面を被覆し、熱交換器の管を構成する合金を
前記の層によつて隠蔽するならば、熱交換器の内
部における汚染が低減及び（又は）阻止され、従
つて外殻−管式熱交換器の操業可能時間を著るし
く延長しうることが今回見いだされた。 If the inner surface of the heat exchanger tubes is coated with an inert layer that is impermeable to substances in the reaction tube effluent that cause contamination, and the alloy constituting the heat exchanger tubes is coated with said layer, It has now been found that if the heat exchanger is concealed, contamination within the heat exchanger can be reduced and/or prevented and thus the uptime of the shell-and-tube heat exchanger can be significantly extended.
このような層は、反応管流出物に対しては不透
過性であるが、一方では熱の伝達を妨げるほどに
は厚すぎない程度の厚さを有すべきである。 Such a layer should have a thickness that is impermeable to the reaction tube effluent, but not so thick that it impedes heat transfer.
厚さの最低限度は0.5μｍであるが好ましい。ま
た20μｍ以下の厚さを有するのが好ましく、それ
以上厚くすると、層上における温度降下の効果を
極端に大きくしなくてはならない。 The minimum thickness is preferably 0.5 μm. Moreover, it is preferable to have a thickness of 20 μm or less; if it is thicker than that, the effect of temperature drop on the layer must be extremely increased.
本発明の好ましい態様によれば、この層は黒鉛
及び（又は）金属及び（又は）金属酸化物、金属
塩及び（又は）シリケートから実質的になる。 According to a preferred embodiment of the invention, this layer consists essentially of graphite and/or metals and/or metal oxides, metal salts and/or silicates.
この種の層を得るのに用いることができる特に
好適な方法は、粉砕した黒鉛、金属、金属酸化
物、金属塩（一般に粒径＜5μｍ）とシリコーン
基剤樹脂との芳香族溶剤中の粘稠混合物を用いる
ことである。前記混合物を常用の吹付け法で塗布
してから熱硬化させる。熱硬化は、好適には275°
〜375℃の温度下1.5〜５時間で達成される。この
熱硬化（キユアリング）は、溶剤を蒸発させ、樹
脂成分を網状組織に変えるのに必要であり、また
場合によつては樹脂成分を分解させるのに必要で
あるが、珪素は層の中に閉じこめられて残留す
る。この処理の結果として準連続的な層（quasi
−continuous layer）が形成され、この層には小
さな特定の領域（area）が含まれている。この
種の層は摩耗抵抗性にすぐれ、高温にも耐える。 A particularly preferred method that can be used to obtain layers of this type is the viscosity of ground graphite, metals, metal oxides, metal salts (generally particle size <5 μm) and silicone-based resins in an aromatic solvent. By using a thick mixture. The mixture is applied by conventional spraying methods and then heat cured. Heat curing preferably at 275°
Achieved in 1.5-5 hours at a temperature of ~375°C. This thermal curing is necessary to evaporate the solvent and transform the resin component into a network, and in some cases to decompose the resin component, but silicon is not present in the layer. remain confined. This process results in a quasi-continuous layer (quasi
- a continuous layer is formed, which contains small specific areas. This type of layer has good abrasion resistance and can withstand high temperatures.
処理を数回繰返すことにより、層の不透過性を
高めることができる。黒鉛のほかに、周期表の第
族又は第族の金属、例えばアルミニウム、チ
タン、ジルコニウム及びそれらの酸化物も利用で
きる。またシリケート及びアルミネートを用いる
こともできる。 By repeating the treatment several times, the impermeability of the layer can be increased. Besides graphite, metals from groups or groups of the periodic table can also be used, such as aluminum, titanium, zirconium and their oxides. Silicates and aluminates can also be used.
特に黒鉛及びアルミニウムはいずれも廉価であ
つて、しかも施用が容易であるにも拘らず、それ
らを用いると所望の成果〔汚染現象の低減及び
（又は）抑制〕が得られる。すなわちシリコーン
樹脂中に黒鉛又はアルミニウムの粒子を添加する
ことにより、被覆層の多孔度を低下させて汚染物
質の促進剤の拡散を低下させ、被覆層の金属表面
への接着性を向上させ、熱の伝達を改良する、等
の効果が達成される。シリコーン樹脂単独ではこ
のような効果は達成されない。 In particular, graphite and aluminum are both inexpensive and easy to apply, yet their use provides the desired results (reduction and/or suppression of pollution phenomena). In other words, the addition of graphite or aluminum particles to the silicone resin reduces the porosity of the coating layer, reduces the diffusion of contaminant accelerators, improves the adhesion of the coating layer to metal surfaces, and improves thermal resistance. Effects such as improving the transmission of information are achieved. Silicone resins alone do not achieve these effects.
金属層を施すのに用いうる他の方法には、減圧
下での蒸発（真空めつき又は真空蒸着）、蒸気状
の金属の分解による金属沈積層の形成（ガスめつ
き）といつた慣用技法がある。 Other methods that can be used to apply the metal layer include conventional techniques such as evaporation under reduced pressure (vacuum plating or vacuum evaporation) and formation of a metal deposit by decomposition of the metal in vapor form (gas plating). There is.
本発明の第二の態様によると、熱交換器の管の
内面上の不透過層は不活性なポリマー層で構成さ
れる。 According to a second aspect of the invention, the impermeable layer on the inner surface of the tubes of the heat exchanger is composed of an inert polymer layer.
このポリマー層は、分解反応管からの流出物を
冷却する際に回収される油性留分（エチレンクエ
ンチ油）と、遊離ラジカル形成開始剤、特に過酸
化ベンゾイル、ヒドロ過酸化クメンのごとき過酸
化物との混合物を管の内面に塗布し、過剰分を流
し去つた後に残る混合物を熱硬化させて形成され
た層であることが好ましい。油性留分はビニル置
換基を有し、ラジカル形成開始剤の存在により網
目構造の生成反応が促進され、完結して良好な性
質（有孔度が低く、熱電導度が大きい）のポリマ
ーの薄層が得られる。 This polymer layer combines the oily fraction (ethylene quenched oil) recovered during cooling of the effluent from the cracking reactor tube and free radical formation initiators, particularly peroxides such as benzoyl peroxide and cumene hydroperoxide. It is preferable that the layer is formed by applying a mixture with the inner surface of the tube to the inner surface of the tube, and heat curing the mixture that remains after the excess is washed away. The oily fraction has vinyl substituents, and the presence of a radical-forming initiator accelerates the network structure formation reaction, resulting in a thin film of polymer with good properties (low porosity and high thermal conductivity). You get layers.
このような層は、通常現われる汚染層にきわめ
て類似した構造を有し、熱交換器内を支配してい
る温度に対して安定であるため、熱交換器内に現
われる現象に影響を及ぼすことがない。この種の
層がいつたん形成されると、その上には薄い汚染
層が生じるにすぎない。 Such a layer has a structure very similar to the normally occurring contaminant layer and is stable with respect to the temperature prevailing in the heat exchanger, so that it cannot influence the phenomena occurring in the heat exchanger. do not have. Once this type of layer is formed, only a thin layer of contamination forms above it.
また、本発明は、炭化水素出発物質をアルケン
に分解するための装置に用いられる外殻−管式熱
交換器であつて、アルケン製造用の分解加熱炉の
反応管流出物を透過させない不活性な層によつて
熱交換器の管の内面が被覆され、熱交換器の管を
構成している合金が前記の層によつて隠蔽されて
いるような熱交換器に関するものである。 The present invention also provides a shell-tube heat exchanger used in an apparatus for decomposing hydrocarbon starting materials into alkenes, the inert heat exchanger being impermeable to the reaction tube effluent of a cracking furnace for producing alkenes. The present invention relates to a heat exchanger in which the inner surface of the tubes of the heat exchanger is coated with a layer such that the alloy constituting the tubes of the heat exchanger is hidden by said layer.
熱交換器の管の内面を被覆する層は、好ましく
は前述した条件に合致すべきである。 The layer covering the inner surface of the tubes of the heat exchanger should preferably meet the conditions mentioned above.
また本発明は、炭化水素出発物質をアルケンに
分解するための装置に用いられ、かかる装置の分
解反応管からの流出物の冷却処理に耐える外殻−
管式熱交換器を製造する方法であつて、分解反応
管からの流出を冷却する際に回収される油性留分
（アルキレンクエンチ油）と遊離ラジカル形成開
始剤との混合物を該熱交換器の管の内面上に吹付
け、それを熱硬化させることによつてポリマー層
を形成する前記の方法に関するものである。 The present invention also provides an outer shell for use in apparatus for cracking hydrocarbon starting materials to alkenes, which withstands the cooling treatment of the effluent from the cracking reaction tube of such apparatus.
A method of manufacturing a tubular heat exchanger, the method comprising: adding a mixture of an oily fraction (alkylene quench oil) recovered during cooling of the effluent from a cracking reaction tube and a free radical forming initiator to the tube heat exchanger. The above method involves forming a polymer layer by spraying it onto the inner surface of a tube and curing it thermally.
アルケン及びアルケン混合物を重合させるには
過酸化物が有効な触媒であるため、前記の方法で
は触媒として過酸化物、特に過酸化ベンゾイルを
用いるのが好ましい。 Since peroxides are effective catalysts for polymerizing alkenes and alkene mixtures, it is preferred to use peroxides, especially benzoyl peroxide, as catalysts in the above process.
触媒の量は広範囲に亘つて変えられるが、0.5
〜３％の触媒が含まれている混合物を使用するの
が好ましく、このような混合物を用いると良好な
ポリマー層をすみやかに得ることができる。 The amount of catalyst can be varied over a wide range, but 0.5
Preference is given to using mixtures containing ~3% of catalyst, with which good polymer layers can be readily obtained.
以下例を挙げて、本発明による装置を用いて得
られる効果を示す。 The following examples illustrate the effects obtained using the device according to the invention.
例
年産エチレン40000トンの能力を有する現用の
エチレン製造装置を用いて軽油の分解を行つた。
分解加熱炉からの流出物の組成は次のとおりであ
つた。Example: Light oil was cracked using a current ethylene production facility with an annual production capacity of 40,000 tons of ethylene.
The composition of the effluent from the decomposition furnace was as follows.
流出物の組成（重量％）
H2 0.49
CH4 8.21
CO 0.02
8.72
C2H2 0.16
C2H4 21.22
C2H6 2.87
24.25
メチル−アセチル 0.16
プレパジエン 0.12
C3H6 13.61
C3H8 0.41
14.30
C4H6 4.86
C4H8 6.57
C4H10 0.05
11.48
〜C5 6.21
ベンゼン 2.82
C6（NA） 2.05
トルエン 2.22
C7（NA） 0.67
ｏ−キシレン 0.26
ｍ−キシレン 0.43
ｐ−キシレン 0.20
エチルベンゼン 0.32
スチレン 0.40
C8（NA） 0.15
〜C9 2.68
C10≦ 11.83
41.25
100.0
NA＝非芳香族
並列に連結した２基の洗浄したての外殻−管式
熱交換基（TLX）内において、800〜850℃の温
度及び1.6baraの圧力を有する前記の流出物を冷
却し、その間熱交換器の外殻側で110baraの圧力
を有する水蒸気を発生させた。Composition of leakage (weight %) H 2 0.49 CH 4 8.02 8.02 8.72 C 2 H 2 H 2 h 6 21.22 C 2 H 6 2.87 Methyl -acetyl 0.16 Prepajenen 0.12 C 3h 6 13.61 C 3 H 8 0.41 14.41 14.30 C 4 H 6 4.86 C 4 H 8 6.57 C 4 H 10 0.05 11.48 ~C 5 6.21 Benzene 2.82 C 6 (NA) 2.05 Toluene 2.22 C 7 (NA) 0.67 o-xylene 0.26 m-xylene 0.43 p-xylene 0.20 Ethylbenzene 0 .32 Styrene 0.40 C 8 (NA) 0.15 ~ C 9 2.68 C 10 ≦ 11.83 41.25 100.0 NA = non-aromatic In two freshly cleaned shell-to-tube heat exchange groups (TLX) connected in parallel, 800 ~ The effluent with a temperature of 850° C. and a pressure of 1.6 bara was cooled while steam with a pressure of 110 bara was generated on the shell side of the heat exchanger.
一方のTLX(A)は、このタイプの管に常用され
るニツケル−クロム合金製の熱交換用の管を有す
るものであつた。 The TLX (A), on the other hand, had heat exchange tubes made of nickel-chromium alloy, which is commonly used for this type of tube.
他のTLX(B)は、同じニツケル−クロム合金製
であるが、その内面に３工程で塗布された厚さ
5μｍのアルミニウム基剤層が被覆された熱交換
用の管を有するものであつた。 The other TLX (B) is made of the same nickel-chromium alloy, but with a thickness applied to its inner surface in three steps.
It had a heat exchange tube coated with a 5 μm aluminum base layer.
試験の開始時点におけるTLX(A)からの冷却さ
れた流出物の温度は420℃であり、そしてTLX(B)
からの冷却された流出物の温度は450℃であつた。 The temperature of the cooled effluent from TLX (A) at the beginning of the test is 420 °C, and the temperature of TLX (B)
The temperature of the cooled effluent from was 450°C.
時間の経過に対する両TLXからの流出物の温
度の変化が図面に示されている。 The change in temperature of the effluent from both TLXs over time is shown in the figure.
曲線ＡはTLX(A)についての結果を示し、曲線
ＢはTLX(B)についての結果を示すものである。 Curve A shows the results for TLX(A), and curve B shows the results for TLX(B).
TLX(A)（曲線Ａ）の場合、TLXからの流出物
の温度が約５日間で500℃に上昇し、それ以後の
試験期間中に温度は斬次上昇を続け、26日後には
許容最高温度の560℃に達することが図から明ら
かである。 In the case of TLX(A) (curve A), the temperature of the effluent from the TLX rose to 500°C in about 5 days, and the temperature continued to rise steadily during the subsequent test period, reaching the allowable maximum after 26 days. It is clear from the figure that the temperature reaches 560℃.
TLX(B)（曲線Ｂ）の汚染速度は実質的に一定
不変であつて、連続可能操作時間は、TLX(A)の
26日の代りに60日という値が外挿法で求められ
る。 The contamination rate of TLX(B) (curve B) is virtually constant, and the continuous operation time is the same as that of TLX(A).
The value of 60 days instead of 26 days is determined by extrapolation.
このことから、第２のTLXによる全試験期間
を通じての熱伝達率が第１のTLXによるよりも
すぐれていたことが明らかである。 From this, it is clear that the heat transfer coefficient of the second TLX throughout the entire test period was superior to that of the first TLX.
両TLXを操作系から外して検査した。 Both TLXs were removed from the operating system and inspected.
TLX(A)は厚い汚染層を含んでいるように見う
けられた。 TLX(A) appeared to contain a thick layer of contamination.
TLX(B)にはわずかな汚染が認められたにすぎ
なかつた。 Only slight contamination was observed in TLX(B).
粒径2μｍ未満の粉末アルミニウム12重量％、
メチル基とフエニル基とを含むシリコーン樹脂48
重量％、及びトルエン40重量％の混合物を管の中
に吹付け、過剰の混合物を流し去り、そして残つ
た層を300℃で２時間加熱してトルエンを蒸発さ
せると共に樹脂を網状組織となし、この工程をさ
らに１回繰返し、そして粒径2μｍ未満の粉末ア
ルミニウム10重量％、同じシリコーン樹脂40重量
％、及びトルエン50重量％の混合物による処理を
最後に１回繰返すことにより、TLX(B)の熱交換
用の管の内面に対する被覆を行つた。 12% by weight of powdered aluminum with a particle size of less than 2 μm,
Silicone resin containing methyl group and phenyl group 48
% by weight and 40% by weight toluene into the tube, the excess mixture was poured off, and the remaining layer was heated at 300° C. for 2 hours to evaporate the toluene and create a network of resin; This process was repeated one more time and one final treatment with a mixture of 10% by weight powdered aluminum with particle size <2 μm, 40% by weight of the same silicone resin, and 50% by weight toluene produced TLX(B). The inner surface of a heat exchange tube was coated.
例
TLX(C)を用いて例の試験を繰返した。TLX
(C)の熱交換用の管の内側には、黒鉛を基剤とする
厚さ5μｍの層からなる被覆が下記のようにして
施された。Example The test of the example was repeated using TLX(C). T.L.X.
On the inside of the heat exchange tube (C), a coating consisting of a graphite-based layer with a thickness of 5 μm was applied as follows.
粒径1μｍ未満の黒鉛24重量％、例で被覆を
形成するのに用いたと同じシリコーン樹脂36重量
％、及びトルエン40重量％からなる混合物を管内
に導入し、過剰分を流し去り、そして残つた層を
300℃で２時間加熱した。この温度においてトル
エンは蒸発し、樹脂は網状組織に変わつた。この
処理を１回繰返したうえ、粒径1μｍ未満の黒鉛
20重量％、同じシリコーン樹脂30重量％及びトル
エン50重量％の混合物による処理をさらに１回最
終的に繰返した。 A mixture consisting of 24% by weight of graphite with a particle size of less than 1 μm, 36% by weight of the same silicone resin used to form the coating in the example, and 40% by weight of toluene was introduced into the tube, the excess was poured off, and the remaining layer
Heated at 300°C for 2 hours. At this temperature the toluene evaporated and the resin turned into a network. After repeating this process once, graphite with a particle size of less than 1 μm
The treatment was repeated one further final time with a mixture of 20% by weight, 30% by weight of the same silicone resin and 50% by weight of toluene.
時間の経過に対するこのTLX(C)からの流出物
の温度の変化は、TLX(B)（例）からの流出物
の温度の経時変化と一致した。 This change in temperature of the effluent from TLX(C) over time was consistent with the change in temperature of the effluent from TLX(B) (example) over time.
試験終了時に熱交換用の管の検査を行つたが、
わずかな汚染が認められたにすぎなかつた。 At the end of the test, the heat exchange tubes were inspected, but
Only slight contamination was observed.
例
例におけると同じ試験を行つたが、本例にお
いてはTLX(D)を用いた。このTLX(D)の熱交換用
の管の内面には、分解反応管からの流出物を冷却
する際に得られる油性留分（エチレンクエンチ
油）と1.5％の過酸化ベンゾイルとを混合し、こ
の混合物を熱交換用の管内に導入し、過剰分を流
し去つてから管を400℃に外部から加熱すること
によつて形成されたポリマー層が被覆されてい
た。Example The same test as in Example was conducted, but in this example TLX(D) was used. On the inner surface of the heat exchange tube of this TLX (D), an oily fraction (ethylene quench oil) obtained when cooling the effluent from the cracking reaction tube and 1.5% benzoyl peroxide are mixed. This mixture was introduced into a heat exchange tube and coated with a polymer layer formed by externally heating the tube to 400.degree. C. after flushing off the excess.
TLX(D)からの流出物の温度の変化も図の曲線
Ｂと一致した。試験が終わつた時点でTLX(D)の
熱交換用の管を検査した。わずかに汚染層がポリ
マー層の上に沈積していた。 The change in temperature of the effluent from TLX(D) also coincided with curve B in the figure. At the end of the test, the TLX(D) heat exchange tubes were inspected. A slight contamination layer was deposited on top of the polymer layer.
図面は、従来技法による熱交換器からの流出物
の温度の経時変化（曲線Ａ）と本発明による熱交
換器からの流出物の温度の経時変化（曲線Ｂ）と
を比較したグラフである。
The figure is a graph comparing the time course of the temperature of the effluent from a heat exchanger according to the prior art (curve A) and the time course of the effluent from a heat exchanger according to the invention (curve B).
Claims (1)
れた分解加熱炉、及び該加熱炉に連結した、反応
管流出物を冷却するのに用いられ、外殻側で水蒸
気を発生させる外殻−管式熱交換器（「クエンチ」
クーラー、「トランスフアーライン」熱交換器、
TLX）を包含する、炭化水素出発物質をアルケ
ンに熱分解するための装置（プラント）におい
て、汚染の原因となる反応出物中の物質に敏感で
なく、しかもこれを透過させない層によつて該熱
交換器の管の内面が被覆され、かつ該層は、シリ
コーン樹脂中の黒鉛又はアルミニウムの粒子の混
合物から形成されたものであることを特徴とする
前記の装置。 ２ 該被覆層が、アルミニウムの粒子とシリコー
ン樹脂の混合物から形成されたものであることを
特徴とする特許請求の範囲１に記載の装置。 ３ 外側から加熱される反応管（コイル）が含ま
れた分解加熱炉、及び該加熱炉に連結した、反応
管流出物を冷却するのに用いられ、外殻側で水蒸
気を発生させる外殻−管式熱交換器（「クエンチ」
クーラー、「トランスフアーライン」熱交換器、
TLX）を包含する、炭化水素出発物質をアルケ
ンに熱分解するための装置（プラント）におい
て、汚染の原因となる反応出物中の物質に敏感で
なく、しかもこれを透過させない層によつて該熱
交換器の管の内面が被覆され、かつ該層は、該熱
分解管からの流出物を急冷する際に回収される油
性留分（アルキレンクエンチ油）と遊離ラジカル
形成開始剤との混合物を該管の内側の表面に、例
えば吹き付けによつて塗布し、その後該被覆層を
熱硬化させることによつて形成されたポリマー層
であることを特徴とする前記の装置。 ４ 該ポリマー層が、該分解反応器からの流出物
を急冷する際に回収される油性留分、及び開始剤
としての過酸化物との混合物を塗布し、その後被
覆層を熱硬化させることによつて形成されたもの
であることを特徴とする特許請求の範囲２に記載
の装置。[Claims] 1. A decomposition heating furnace including a reaction tube (coil) heated from the outside, and a decomposition heating furnace connected to the heating furnace, which is used for cooling the reaction tube effluent, and which generates water vapor on the outer shell side. A shell-to-tube heat exchanger (“quench”) that generates
Cooler, “transfer line” heat exchanger,
In plants for the pyrolysis of hydrocarbon starting materials to alkenes, including the Device as described above, characterized in that the inner surface of the tubes of the heat exchanger is coated, and that the layer is formed from a mixture of graphite or aluminum particles in a silicone resin. 2. The device according to claim 1, wherein the coating layer is formed from a mixture of aluminum particles and silicone resin. 3. A decomposition heating furnace containing a reaction tube (coil) heated from the outside, and an outer shell connected to the heating furnace, used for cooling the reaction tube effluent and generating steam on the outer shell side. Tubular heat exchanger (“quench”)
Cooler, “transfer line” heat exchanger,
In plants for the pyrolysis of hydrocarbon starting materials to alkenes, including the The inner surface of the tubes of the heat exchanger is coated, and the layer contains a mixture of an oily fraction (alkylene quenched oil) recovered during quenching the effluent from the pyrolysis tube and a free radical forming initiator. A device as defined above, characterized in that it is a polymer layer formed by applying it to the inner surface of the tube, for example by spraying, and then curing the coating layer thermally. 4. The polymer layer is coated with a mixture of an oily fraction recovered during quenching of the effluent from the cracking reactor and peroxide as an initiator, followed by heat curing of the coating layer. 3. A device according to claim 2, characterized in that it is formed by:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8204731 | 1982-12-07 | ||
| NL8204731A NL8204731A (en) | 1982-12-07 | 1982-12-07 | INSTALLATION FOR THERMAL CRACKING OF A HYDROCARBON OUTPUT MATERIAL TO OLEGINS, TUBE HEAT EXCHANGER USED IN SUCH INSTALLATION AND METHOD FOR MANUFACTURING A TUBE HEAT EXCHANGER. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59157494A JPS59157494A (en) | 1984-09-06 |
| JPH0519080B2 true JPH0519080B2 (en) | 1993-03-15 |
Family
ID=19840709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23121983A Granted JPS59157494A (en) | 1982-12-07 | 1983-12-07 | Device for pyrolyzing hydrocarbon and shell-tube type heat exchanger used for said device and manufacture thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0110486B1 (en) |
| JP (1) | JPS59157494A (en) |
| CA (1) | CA1210282A (en) |
| DE (1) | DE3368282D1 (en) |
| NL (1) | NL8204731A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1248980B (en) * | 1990-06-22 | 1995-02-11 | Nuovo Pignone Spa | PERFECTED COPPER HEAT EXCHANGER FOR WALL BOILERS |
| US5805973A (en) * | 1991-03-25 | 1998-09-08 | General Electric Company | Coated articles and method for the prevention of fuel thermal degradation deposits |
| AU667945B2 (en) * | 1992-09-22 | 1996-04-18 | General Electric Company | Coated articles and method for the prevention of fuel thermal degradation deposits |
| CA2105188A1 (en) * | 1992-09-22 | 1994-03-23 | George A. Coffinberry | Coated article for hot hydrocarbon fluid and method of preventing fuel thermal degradation deposits |
| CA2113366C (en) * | 1993-01-15 | 2005-11-08 | George A. Coffinberry | Coated articles and method for the prevention of fuel thermal degradation deposits |
| DE4334827C1 (en) * | 1993-10-08 | 1994-10-06 | Mannesmann Ag | Process for decreasing the coking of heat exchange surfaces |
| DE4405884C1 (en) * | 1994-02-21 | 1995-09-07 | Mannesmann Ag | Heat exchange surface in reactors and / or heat exchangers and method for producing a catalytically deactivated metal surface |
| US6265453B1 (en) * | 1999-07-01 | 2001-07-24 | Syntroleum Corporation | Hydrocarbon conversion system with enhanced combustor and method |
| JP2001330394A (en) * | 2000-05-22 | 2001-11-30 | Denso Corp | Exhaust gas heat exchanger |
| CN103968689A (en) * | 2014-05-26 | 2014-08-06 | 英尼奥斯欧洲股份公司 | Waste water cooler used in acrylonitrile manufacture |
| CN112881559B (en) * | 2021-01-20 | 2023-08-18 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Method for rapidly detecting phthalate content |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4997949A (en) * | 1973-01-26 | 1974-09-17 | ||
| JPS501446A (en) * | 1973-05-09 | 1975-01-09 | ||
| JPS5125414A (en) * | 1974-08-28 | 1976-03-02 | Showa Aluminium Co Ltd | NETSUKOKANKYOTAISHOKUARUMINIUMUAWASEZAI |
| JPS55129490A (en) * | 1979-03-22 | 1980-10-07 | Chevron Res | Dirt prevention for heat converter |
| JPS5620998A (en) * | 1979-06-28 | 1981-02-27 | Resistoflex Corp | Anticorrosion heat exchanger element and assembly method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL300760A (en) * | ||||
| BE348252A (en) * | ||||
| DE1071105B (en) * | 1956-12-27 | |||
| NL162991C (en) * | 1970-05-25 | 1980-07-15 | Shell Int Research | METHOD AND APPARATUS FOR Deterring gas mixtures. |
| DE2412421A1 (en) * | 1974-03-15 | 1975-09-25 | Schmidt Sche Heissdampf | HEAT EXCHANGER WITH DOUBLE PIPE ELEMENTS |
| US4054174A (en) * | 1974-03-18 | 1977-10-18 | The Babcock & Wilcox Company | Method of inhibiting deposition of internal corrosion products in tubes |
| JPS5950269B2 (en) * | 1980-05-23 | 1984-12-07 | 住友軽金属工業株式会社 | Coating composition for corrosion protection on the inner surface of heat exchanger tubes |
-
1982
- 1982-12-07 NL NL8204731A patent/NL8204731A/en not_active Application Discontinuation
-
1983
- 1983-12-06 EP EP19830201725 patent/EP0110486B1/en not_active Expired
- 1983-12-06 DE DE8383201725T patent/DE3368282D1/en not_active Expired
- 1983-12-06 CA CA000442653A patent/CA1210282A/en not_active Expired
- 1983-12-07 JP JP23121983A patent/JPS59157494A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4997949A (en) * | 1973-01-26 | 1974-09-17 | ||
| JPS501446A (en) * | 1973-05-09 | 1975-01-09 | ||
| JPS5125414A (en) * | 1974-08-28 | 1976-03-02 | Showa Aluminium Co Ltd | NETSUKOKANKYOTAISHOKUARUMINIUMUAWASEZAI |
| JPS55129490A (en) * | 1979-03-22 | 1980-10-07 | Chevron Res | Dirt prevention for heat converter |
| JPS5620998A (en) * | 1979-06-28 | 1981-02-27 | Resistoflex Corp | Anticorrosion heat exchanger element and assembly method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0110486B1 (en) | 1986-12-10 |
| EP0110486A1 (en) | 1984-06-13 |
| CA1210282A (en) | 1986-08-26 |
| JPS59157494A (en) | 1984-09-06 |
| NL8204731A (en) | 1984-07-02 |
| DE3368282D1 (en) | 1987-01-22 |
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