A7 311147 __B7 五、發明説明（1 ) ' 本發明係關於烴類熱裂解的方法。更特定而言，本發明 係有關於烴類熱裂解間產生的煤焦之剝落的促進方法。 在產生稀' fe化合物的方法中，含有飽和碳氫化合物如乙 炊、丙燒、丁虎、戊烷、輕油、或是關於上述提及的兩種 或更多種混合物的流體，進料至熱裂解（熱解）爐中。稀釋 用流體’如蒸氣’經常與碳氫化合物進料一起導入裂解墟 0 於裂解壚中，飽和碳氫化合物會轉變成晞烴化合物。例 如，乙烷流導入裂解爐，在其中被轉變成乙缔和少量其它 的碳氫化合物。例如’丙烷流導入裂解壚，在其中被轉變 成乙烯和丙烯，及少量其它的碳氫化合物。同樣地，含有 乙烷、丙烷、丁烷、戊烷和輕油的碳氫化合物之混合物， 導入裂解爐後，在其中被轉變成含有乙烯、丙烯、丁埽、 戊晞和奈的缔烴化合物混合物，烯烴化合物是工業化學中 重要的一類。例如，乙烯爲用以製造聚乙烯的單體或共聚 單體。對於熟知此項技藝的人士，晞烴化合物的其他用 是眾所皆知的β 1 烴類熱裂解的結果，此裂解產物氣流亦含有相當量的氳 氣、甲烷、乙烯、—氧化碳、二氧化碳、和其他非缔烴 的熱裂解產物0 1‘ 當烴類熱解或熱裂解時，會形成一種稱爲"煤焦，，的半純 碳。形成於裂解過程的煤焦，通常澱積在此方法用的熱裂 解爐的裂解管之表面0煤焦積聚於裂解管的表面上，最後 需要將裂解壚關機，以便燒掉煤焦殿積物。由於澱積的煤 本纸張尺度適用中國國WiCNS)7^72l〇x 297^) (碕先閱讀背面之注意事項再填寫本頁) 裝 訂 經濟部中央標準局員工消費合作社印製 B7 五、發明説明（2 ) 焦具有熱絕緣性的結果，使得裂解管内的壓力過度下降且 需要較高的鍋爐溫度’因此煤焦澱積物的積聚將迫使裂解 爐必須週期性的關機。 已知爲防垢劑的組合物’已用來抑制煤焦澱積物形成於 裂解爐管路的表面，以及下游的熱交換器和其他處理設備 f 的金屬表面上。雖然可利用防垢劑來抑制煤焦的形成，但 在烴類裂解時煤焦仍會以緩慢的速度累積。減少煤焦累積 或殿積於裂解管表面是値得的。減少積聚在裂解管上的煤 焦’將可增長裂解爐關機之間的運轉時間，並因而改善裂 解操作。 ° 根據本發明，可藉由在適當裂解條件下操作的熱裂解爐 輸送經類氣體，以產生裂解的產物氣禮，來促進在烴類氣 體熱裂解間產生的煤焦之剝落。一種含有錫但不含碎的抗 垢劑，可適量加入烴類氣體中，而足以促進烴類氣體熱裂 解間產生的煤焦之剝落。 — '' 經濟部中央標率局員工消費合作杜印製 (請先閲讀背面之注意事項再填寫本頁) 本發明另一方面包含，將一種含有錫但不含矽的抗垢劑 ，在適當的處理條件下與熱裂解壚的管路接觸，以提供— 已處理的管路。烴類氣體送經此一在適當裂解條件下操作 的已處理管路，以產生其f具有剝落煤焦的裂解產物。 本發明將以附圖爲參考資料，其中： 圖1爲原理圖’顯示乙婦裂解過程，其中包含裂解爐裝置 和此新穎方法的其他元件； 圖2爲長條圖’表示乙烷裂解間，從以二甲基硫，锡，或 錫/碎處理過的HK4M合金管中剝落的煤焦量；及 -5- 本紙張尺度適用中國國家標準（（：]^),\4規格（210><29?公釐A7 311147 __B7 V. Description of the invention (1) 'The present invention relates to a method for thermal cracking of hydrocarbons. More specifically, the present invention relates to a method for promoting the peeling of coal char produced during thermal cracking of hydrocarbons. In the method of producing dilute Fe compounds, fluids containing saturated hydrocarbons such as ethyl ethane, propane, butyl tiger, pentane, light oil, or two or more mixtures mentioned above are fed Into the pyrolysis (pyrolysis) furnace. Dilution fluids, such as steam, are often introduced into the cracking zone together with the hydrocarbon feed. In the cracking zone, the saturated hydrocarbons will be converted into hydrocarbon compounds. For example, the ethane stream is introduced into a cracking furnace, where it is converted into ethylene and small amounts of other hydrocarbons. For example, the 'propane stream is introduced into the cracker, where it is converted into ethylene and propylene, and small amounts of other hydrocarbons. Similarly, a mixture of hydrocarbons containing ethane, propane, butane, pentane, and light oil is introduced into the cracking furnace, where it is converted into an associative hydrocarbon compound containing ethylene, propylene, butylene, ammonium, and naphthalene. Mixtures, olefin compounds are an important class in industrial chemistry. For example, ethylene is a monomer or comonomer used to make polyethylene. For those familiar with this technique, other uses of hydrocarbon compounds are the result of the well-known thermal cracking of β 1 hydrocarbons. This cracked product gas stream also contains considerable amounts of radon gas, methane, ethylene, carbon oxide, and carbon dioxide. , And other non-associated thermal cracking products 0 1 'When hydrocarbons are pyrolyzed or thermally cracked, a semi-pure carbon called "coal char" is formed. The coal char formed in the cracking process is usually deposited on the surface of the cracking tube of the thermal cracking furnace used in this method. Coal char accumulates on the surface of the cracking tube. Finally, the cracking furnace needs to be shut down in order to burn off the coal coke deposits. The standard of the deposited coal-based paper is applicable to the Chinese WiCNS) 7 ^ 72l〇x 297 ^) (Only read the precautions on the back and then fill out this page) B7 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Inventions Explanation (2) As a result of the thermal insulation of the coke, the pressure in the cracking tube drops excessively and requires a high boiler temperature. Therefore, the accumulation of coal char deposits will force the cracking furnace to be shut down periodically. Compositions known as antifouling agents have been used to inhibit the formation of coal char deposits on the surface of the cracking furnace piping, as well as on the metal surfaces of downstream heat exchangers and other processing equipment f. Although scale inhibitors can be used to inhibit the formation of coal scorch, coal scorch will accumulate at a slow rate during the cracking of hydrocarbons. It is possible to reduce the accumulation of coal scorch or build up on the surface of the cracking tube. Reducing the coal char accumulated on the cracking tube will increase the operating time between the shutdown of the cracking furnace and thus improve the cracking operation. ° According to the present invention, the pyrolysis furnace operated under appropriate cracking conditions can be used to transport the passing gas to produce the cracked product gas, which can promote the peeling of coal char produced during the thermal cracking of hydrocarbon gas. An anti-scaling agent containing tin but not broken, can be added to the hydrocarbon gas in an appropriate amount, which is enough to promote the peeling of coal char produced during the thermal cracking of the hydrocarbon gas. — ”Printed by the Ministry of Economic Affairs, Central Bureau of Standards and Quotations and Employee ’s Consumer Cooperation (please read the precautions on the back and then fill out this page) The other aspect of the present invention includes the inclusion of an anti-scaling agent containing tin but not silicon. Under the conditions of the treatment, contact with the pyrolysis pipeline to provide-treated pipeline. The hydrocarbon gas is passed through this treated pipeline operating under appropriate cracking conditions to produce a cracked product whose f has exfoliated coal char. The present invention will refer to the accompanying drawings, in which: Figure 1 is a schematic diagram 'showing the cracking process of a woman, which includes a cracking furnace device and other components of this novel method; Figure 2 is a bar graph' showing the ethane cracking room, The amount of coal char peeled off from HK4M alloy tubes treated with dimethyl sulfide, tin, or tin / crush; and -5- This paper scale is applicable to the Chinese National Standard ((:) ^), \ 4 specifications (210 > < 29? mm
:第^71^365號專利申請案 %中書修正頁(86年5月） 五、發明説明（3 ) A7 B7 圖3爲長條圖’表示乙烷裂 久奸間，從以二甲基硫 錫/矽處理過的Η P改良合金管中剝落的煤：、 錫，或 經濟部中央標準局員工消費合作社印製 10 代表裂解爐部分 12 代表裂解爐； 14 代表對流區； 16 代表散熱區； 18 代表管線； 20 代表管線； 22 代表線管； 24 代表線管； 26 代表分離器； 28 代表線管； 3 0 代表線管； 32 代表線管； 34 代表燃燒器； 3 6 代表管線；及 3 8 代表熱交換器。 本發月的方法係關於烴類熱裂解以產生所需的烴類終產物 將烴類氣體供给或充滿至熱裂解裝置，在其中烴類氣體遭 -6 本紙張尺度適用中國國家標準（CNS)从祕 os7公瘦 裝 訂 (請先閱讀背面之注意事項再填寫本頁) · · 正 姆li繼: £_〇_) 10365號專利申請案 !月書修正頁(86年5月） A7 B7 經濟部中央標準局貝工消費合作社印製 五、發明説明（4 ) 受一酷熱，高溫的環境以產生裂解的氣體。此烴類氣體可包 含任一類適於熱裂解成晞烴化合物的烴類。然而，較佳的烴 類氣體可包含自下列各物中選出的石蠟烴類，包括乙烷，丙 烷，丁烷，戊烷，輕油，或是關於上述提及的任兩種或更多 種的混合物。輕油一般被認爲是一種複雜的烴類混合物，其 具有的沸點範圍，以美國材料試驗學會（ASTM)的標準試驗 方法測試，從約1 8 0 T至約4 0 0 °F。 本發明另一特色爲，此一被充入熱裂解裝置的烴類進料， 在進入熱裂解爐裝置前可以充分地與依烯釋劑混合。此稀釋 劑具有數個正面的功用，其中之一包括提供熱裂解裝置内良 好的反應條件，以產生所需的反應終產物。稀釋劑藉著提供 一較低的烴類進料流體分壓，因減少不要的反應產物（如氫 氣，甲規·）的量，因而增加獲得所需的烴類產物之裂解反應 必要性，而達成此一功用。此外，由於混合稀釋流體而造成 的較低分壓，可使形成於鍋爐管路上的煤焦澱積量降至最低 。雖然任何可提供這些效益的適用流體都可使用，但較佳的 稀釋流體爲氣體。 藉熱裂解爐裝置產生的裂解反應，可發生在任何適合的 溫度，此溫度可提供必要的裂解，以形成所需的終產物或 造成一所需的進料轉化。使用的實際裂解溫度，將視烴類 63j- 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 訂..#- i . ί (請先閲讀背面之注意事項再填寫本頁) 經濟部中央榡率局員工消f合作杜印製 A7 ----S______ 五、發明説明（4 ) 進料氣體的成份和所需的進料轉化而定。 一般而言，裂解溫度可高至2000°F或更高，端視所需的 裂解或轉化量及被裂解進料的分子量。然而，較佳的裂解 溫度將在從約1 2 0 0 °F至約1900°F的範圍。最佳者，裂解溫 度在從1500 T至1800 T的範圍。 e 來自熱裂解爐裝置之裂解的烴類流出物或裂解的烴類或 裂解產物氣體，通常是氣相的烴類混合物。此氣相烴類混 合物，不只包括所需的締煙化合物，如乙烯，丙晞，丁缔 ，和戊烯，同時此裂解的烴類氣體可含有不要的汙染成份 ’包括氧化物和酸化物，和輕的產物和氮氣和甲燒。 本發明方法的裂解爐裝置，可爲此項技藝中已知任何遑 用的熱裂解爐。熟知裂解技術此項技藝的人士皆知不同的 裂解爐，且用於裂解方法適用的裂解壚一般爲偏好的問題 。此裂解壚至少配備一裂解管路以供烴類原料的填充或進 料。此裂解管路提供或界定一個在裂解爐中的裂解區域。 裂解爐作爲釋放所需的熱能，此熱能可提供裂解區中所需 的裂解溫度，以誘發其中的裂解反應。每一裂解管路可具 有任何的相位，能很適當地界定出裂解反應發生的體積， 因此具有一内表面。”裂解溫度”―詞，在此處的定義爲裂 解管所界定的裂解區，其内的溫度。因此，裂解管的外牆 溫度可高於裂解溫度，且因爲熱傳遞的考量，實際上可能 較高。典型在裂解區内的蜃力，一般爲從約〇 psig至約1〇〇 Pdg且較佳從〇 psig至60 psig。 本發明方法提供一種烴類氣體熱裂解間產生的煤焦之剝 •7- 本“家標準(CNS ) ---- (許先閲讀背面之注意事項再填寫本頁) 裝. 訂 A7 B7 3Hl47 五、發明説明（5 ) :的，進万法。已知將裂解爐的管路只以錫化合物處理， 特疋而。’以一種不含矽但含有錫的組成物處理，可你 :煤’、:、的剝落。煤焦的剝落發生在烴類熱裂解間產生的煤 法时著於管路表面以形成—層煤焦，或是其搬積於 管路表面而《平，片裂或折斷此表面時。 、 、對於許多裂解操作而言，並不希望有煤焦剝落，若是剝 落的煤焦會損壞或塞住裂解爐下游的設備、然而，若在下 游設備可處理㈣的煤焦碎片，或提供的裝g適於除去裂 解產物乳財含有之制落煤焦的情沉下，則煤焦剝落的促 進’：使裂解爐管路脱焦間的時間延長；因爲煤焦藉剝落 而自管路表©去除，或避免其M積或附著於管路表面。藉 裂解爐管路脱焦間的時間延長，可縮短鋼爐生產降低時間 ’藉此改進裂解爐產率和產量。因此’若用來處理裂解爐 產物氣體的設備，可處理剝落的煤焦而不損壞，或若能提 供適合的移除或分離装置，以移走裂解產物氣體内至少部 份的剝落煤焦，則煤焦的剝落是可行的。 本迫切發明的重要觀點爲，使用一沒有矽化合物但含有 錫化合物的組成物。已知裂解爐管路根據此處所述的方法 ，只以一錫化合物處理，相對於—含有錫化合物和矽化合 物二者的化合物，非預期地促進煤焦的剥落。另—方面Y 當含有錫與碎组合的组合物，用來處理裂解爐管路時，並 未觀察到煤焦的大量剝落，然而顯示出煤焦的形成和澱積 被抑制。因此，結合錫和梦，可得到某些抗垢劑的優點和 性質’其不同於只含有踢化合物或説是不含矽只含錫的抗 -8 - 本紙張尺度適用中國國家標準（CNS ) A4辦柊ί 210X297公釐） —.---„-----『裝------訂------1 - . ( (請先閱讀背面之注意事項再填寫本頁} 經濟部中央標準局員工消費合作杜印製 A7 五、發明説明（6 ) 垢劑 鲈濟部中央標準局員工消費合作衽印製 任何適合形式的錫都 - A 都了用在不含矽只含錫的抗垢劑組合 物07G素錫，播機錫和古丨人、 啊物和有機錫化合物，及上述任二種 多種的混合物，都爲棋沾-承人 $馬錫的適合來源。"錫，，一詞通常爲這此 錫來源中之任一項。 < 二 於可使用的，些無機錫化合物的實例包括錫氧化物，例如 氧化亞錫和氧化錫；鎮硫化物，例如硫化亞錫和硫化踢. 錫硫酸鹽，例如硫酸亞錫和硫酸錄；踢酸鹽，例如偏錫酸 和硫代錫酸；錫齒化物’例如氟化亞錫，氣化亞錫，澳化 亞錫，碘化亞錫’氟化锡，氣亞錫，漢亞錫和碘亞錫；錫 鱗酸鹽’例如磷酸錫；錫南氧化物如氣氧化亞錫和氣氧化 錫；及錢似物。無機錫化合物中，較佳的踢來源爲不含 鹵素者。 可使用的某些有機踢化合物的實例包括錫碳酸鹽類，例 如甲酸亞錫，醋酸亞錫，丁酸亞錫，辛酸亞錫，癸酸亞錫 ，草酸亞錫，苯甲酸亞錫，和環己烷碳酸亞錫；硫代碳酸 鹽類，例如硫代醋酸亞錫和二硫代醋酸亞錫；二烴基錫雙（ 烴基氫硫基烷氧酸鹽），例如二丁基亞錫雙（異辛基氫硫基 醋酸鹽）和二丙基亞錫雙（丁基氩硫基醋酸鹽）；硫代碳酸錫 類，例如鄰-乙基二硫代碳酸亞錫；碳酸錫類，例如丙基碳 酸亞錫；四烴基鍚化合物，例如，四丁基亞錫，四辛基亞 錫，四癸基亞錫，四-十二烷基亞錫，和四苯基亞錫；二烴 基踢氧化物，例如，二丙基亞錫氧化物，二丁基亞錫氧化 物’二辛基亞錫氧化物，和二苯基亞錫氧化物；二烴基錫 -9· (請先閲讀背面之注意事項再填寫本頁) 裝 訂: No. ^ 71 ^ 365% of the patent application amendment page (May, 86) V. Description of the invention (3) A7 B7 Figure 3 is a bar graph 'representing the cracking of ethane for a long time, from dimethyl Coal peeled in sulfur-tin / silicon treated HP modified alloy tubes :, tin, or printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 10 represents the cracking furnace part 12 represents the cracking furnace; 14 represents the convection zone; 16 represents the heat dissipation zone ; 18 for pipeline; 20 for pipeline; 22 for pipeline; 24 for pipeline; 26 for separator; 28 for pipeline; 30 for pipeline; 32 for pipeline; 34 for burner; 36 for pipeline; And 3 8 represents the heat exchanger. The method of this issue relates to the thermal cracking of hydrocarbons to produce the desired hydrocarbon end products. The hydrocarbon gas is supplied or filled to the thermal cracking device, in which the hydrocarbon gas is subjected to -6. This paper scale is applicable to the Chinese National Standard (CNS) From the os7 male thin binding (please read the precautions on the back before filling in this page) · · Zhengmuli following: £ _〇_) Patent Application No. 10365! Monthly Book Revision Page (May 86) A7 B7 Economy Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry 5. Description of the invention (4) Subject to a very hot, high-temperature environment to produce cracked gas. This hydrocarbon gas may contain any type of hydrocarbons suitable for thermal cracking to a hydrocarbon compound. However, the preferred hydrocarbon gas may include paraffin hydrocarbons selected from the group consisting of ethane, propane, butane, pentane, light oil, or any two or more of the above mentioned mixture. Light oils are generally considered to be a complex hydrocarbon mixture with a boiling point range tested by the American Society for Testing Materials (ASTM) standard test method, from about 180 ° F to about 400 ° F. Another feature of the present invention is that the hydrocarbon feed charged into the thermal cracking device can be fully mixed with the enene release agent before entering the thermal cracking furnace device. This diluent has several positive functions, one of which includes providing good reaction conditions in the thermal cracking unit to produce the desired end product of the reaction. By providing a lower hydrocarbon feed fluid partial pressure, the diluent increases the necessity of the cracking reaction to obtain the desired hydrocarbon product by reducing the amount of unwanted reaction products (such as hydrogen, A gauge), and Achieve this function. In addition, the lower partial pressure caused by mixing the dilution fluids can minimize the amount of coal coke deposits formed on the boiler piping. Although any suitable fluid that provides these benefits can be used, the preferred dilution fluid is gas. The cracking reaction generated by the thermal cracking furnace unit can take place at any suitable temperature. This temperature can provide the necessary cracking to form the desired end product or cause a desired feed conversion. The actual cracking temperature used will depend on the hydrocarbon 63j- This paper scale is compliant with the Chinese National Standard (CNS) A4 specification (210X297 mm) .. #-i. Ί (Please read the precautions on the back before filling this page ) The employees of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs cooperated to print and print the A7 ---- S______ V. Description of the invention (4) The composition of the feed gas and the required feed conversion depend. In general, the cracking temperature can be as high as 2000 ° F or higher, depending on the amount of cracking or conversion required and the molecular weight of the feed to be cracked. However, the preferred cracking temperature will range from about 1 200 ° F to about 1900 ° F. At best, the cracking temperature ranges from 1500 T to 1800 T. e The cracked hydrocarbon effluent or cracked hydrocarbon or cracked product gas from the thermal cracking furnace unit is usually a mixture of hydrocarbons in the gas phase. This gas-phase hydrocarbon mixture includes not only the required associative smoke compounds, such as ethylene, propylene, butylene, and pentene, but also the cracked hydrocarbon gas may contain unwanted pollutants, including oxides and acid compounds, And light products and nitrogen and methane. The cracking furnace device of the method of the present invention may be any thermal cracking furnace known in the art. Those skilled in the art of cracking technology are aware of different cracking furnaces, and the use of cracking methods for cracking methods is generally a matter of preference. This cracking tank is equipped with at least one cracking line for filling or feeding of hydrocarbon feedstock. This cracking line provides or defines a cracking zone in the cracking furnace. The cracking furnace serves to release the required thermal energy, which can provide the required cracking temperature in the cracking zone to induce the cracking reaction therein. Each cracking line can have any phase, which can properly define the volume where the cracking reaction takes place, and therefore has an inner surface. The term "cracking temperature" is defined here as the temperature within the cracking zone defined by the cracking tube. Therefore, the temperature of the outer wall of the cracking tube can be higher than the cracking temperature, and actually may be higher due to heat transfer considerations. The mirage, typically in the cracking zone, is generally from about 0 psig to about 100 Pdg and preferably from 0 psig to 60 psig. The method of the present invention provides a peeling of coal char produced in the thermal cracking of hydrocarbon gases • 7- This "Home Standard (CNS) ---- (Xu first read the precautions on the back and then fill out this page) Pack. Order A7 B7 3Hl47 Fifth, the description of the invention (5): Yes, the tens of thousands method. It is known that the cracking furnace pipeline is only treated with tin compounds, which is special. 'It is treated with a composition that does not contain silicon but contains tin, but you: coal ',:, Peeling. The peeling of coal scorch occurs during the thermal process of hydrocarbon pyrolysis. The coal method is applied to the surface of the pipeline to form a layer of coal scorch, or it is deposited on the surface of the pipeline and is flat and flakes. Or breaking the surface.., For many cracking operations, it is undesirable to have coal char peeling off. If the peeled coal char will damage or plug the equipment downstream of the cracking furnace, however, if the downstream equipment can handle the coal Coke debris, or the supplied g is suitable for removing the cracked coal coke contained in the cracked product milk, the promotion of coal coke spalling ': prolong the time between decoking of the cracking furnace pipeline; Peel off and remove from the pipe surface ©, or avoid its accumulation or adhesion to the pipe surface. The time between the decoking of the cracking furnace pipeline is prolonged, which can shorten the production time of the steel furnace, thereby improving the yield and output of the cracking furnace. Therefore, if the equipment used to treat the product gas of the cracking furnace can deal with the peeled coal char Damage, or if suitable removal or separation devices can be provided to remove at least part of the exfoliated coal char in the cracked product gas, the exfoliation of coal char is feasible. The important point of this urgent invention is to use a silicon-free Compounds but compositions containing tin compounds. It is known that cracking furnace pipes are treated with only a tin compound according to the method described here, relative to compounds containing both tin compounds and silicon compounds, which unexpectedly promotes coal char Exfoliation. Another aspect Y. When the composition containing the combination of tin and crushing was used to treat the cracking furnace pipeline, a large amount of exfoliation of coal char was not observed, but it showed that the formation and deposition of coal char was suppressed. Therefore , Combined with tin and dream, you can get the advantages and properties of certain anti-fouling agents' which is different from the anti--8 containing only kick compounds or silicon-free and tin-only-this paper standard applies to China Standard (CNS) A4 Office (210X297mm) —.--- „-----『 installed ----- order ------ 1-. ((Please read the notes on the back first Refill this page} Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Printed A7 V. Description of the invention (6) Scale agent Employee consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Printed any suitable form of tin-A Silicone-free and tin-only anti-fouling agent composition 07G Su-tin, broadcaster tin and ancient human, organic and organic tin compounds, as well as any two or more of the above mixtures, are all Qi Zhan-Chengren $ 马 锡A suitable source of " tin, " is generally any of this source of tin. ≪ Two, as may be used, examples of some inorganic tin compounds include tin oxides, such as stannous oxide and tin oxide; Town sulfides, such as stannous sulfide and sulfide kick. Tin sulfates, such as stannous sulfate and sulfuric acid; kick salts, such as metastannic acid and thiostannic acid; tin dentate's such as stannous fluoride, gasification Stannous, stannous austenite, stannous iodide 'tin fluoride, stannous gas, stannous tin and stannous iodide; stannic acid salt' such as tin phosphate; tin Southern oxides such as stannous oxide and tin oxide; and money like. Among inorganic tin compounds, the preferred kick source is one that does not contain halogen. Examples of certain organic kick compounds that can be used include tin carbonates such as stannous formate, stannous acetate, stannous butyrate, stannous octoate, stannous caprate, stannous oxalate, stannous benzoate, and cyclic Stannous hexane carbonate; thiocarbonates, such as stannous thioacetate and stannous dithioacetate; dihydrocarbyl tin bis (hydrocarbyl hydrothiothio alkoxide), such as dibutyl stannous bis (iso Octyl hydrothioacetate) and dipropylstannous bis (butyl argon thiothioacetate); tin thiocarbonates, such as o-ethyl stannous dithiocarbonate; tin carbonates, such as propyl Stannous carbonate; tetrahydrocarbyl thorium compounds, for example, tetrabutyl stannous, tetraoctyl stannous, tetradecyl stannous, tetra-dodecyl stannous, and tetraphenyl stannous; dihydrocarbyl kick oxides , For example, dipropyl stannous oxide, dibutyl stannous oxide 'dioctyl stannous oxide, and diphenyl stannous oxide; dihydrocarbyl tin-9 · (please read the notes on the back first (Fill in this page again)
HI I 本紙痕尺度適萌中國國家襟準（CMS > Α4規格（2ΙΟΧ297公釐） 經濟部中央標準局員工消費合作社印製 ^^1147 A7 ----____ 五、發明説明（7 ) 雙（烴基硫醇鹽），例如二丁基亞錫雙（癸基硫醇鹽）；酚類 化合物的錫鹽，例如，亞錫硫代酚鹽；亞錫磺酸鹽例如亞 錫笨磺酸鹽和亞錫-對-甲苯磺鹽；錫胺基曱酸鹽例如亞锡 —乙基胺基胺基甲酸鹽；錫硫代胺基甲酸鹽例如亞錫丙基 硫代胺基甲酸鹽和亞錫二乙基二硫代胺基甲酸鹽；錫亞.嶙 r 酸鹽例如亞錫二苯基亞磷酸鹽；錫磷酸鹽例如亞錫二丙基 磷酸鹽·，錫硫代磷酸鹽例如亞錫〇,〇-二丙基硫代嶙酸鹽 ’亞錫Ο，0 -二丙基二硫代辟酸鹽，錫〇，〇 -二丙基二硫 代磷酸鹽；二烴基錫雙（0,0-雙烴基硫代磷酸鹽）類例如 一 丁基錫雙（〇 ’ 〇 -雙丙基硫代骑酸鹽），及類似物。有機 錫化合物較無機錫化合物爲佳。本發明中以四甲基錫爲較 佳者。 "梦"一詞’用於此處表示秒來源，如元素砂，無機碎化 合物和有機碎化合物，以及上述任二種或更多種的混合物 〇 此處所述的抗垢劑組成物，用於熱裂解爐管路表面之處 理。以此組成物與裂解管表面接觸，可以此抗垢劑，在填 充烴類進料前，預先處理裂解管，或在烴類進料中加入有 效量的抗垢劑來處理裂解管。 可使用任何適於在適合條件下以抗垢劑接觸裂解爐的管 路方法，以提供處理的管路。 用來預先處理裂解爐管路的較佳方法，包括在裂解爐管 路的内襯填充一飽和或稍微過熱，具'有從約3 〇 〇下至約5 〇 〇 T溫度範圍的氣體。管線充填氣體時，裂解爐要燃燒以提 -10- 本紙蒗尺度適用中國國家標準（CNS ) A4規格（21〇X297公釐） (請先閱讀背面之注意事項再填寫本頁〕 裝HI I This paper mark scale is suitable for the Chinese national standard (CMS > Α4 specification (2ΙΟΧ297mm) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy ^^ 1147 A7 ----____ V. Description of invention (7) Double ( Hydrocarbyl mercaptides), such as dibutyl stannous bis (decyl mercaptan); tin salts of phenolic compounds, for example, stannous thiophenolate; Stannous-p-toluenesulfonate; stannyl formate such as stannous-ethylaminocarbamate; tin thiocarbamate such as stannous propylthiocarbamate and Stannous diethyldithiocarbamate; stannous acid salts such as stannous diphenyl phosphite; tin phosphates such as stannous dipropyl phosphate, tin thiophosphates such as Stannous 〇, 〇-dipropyl thiosaltate stannous Ο, 0-dipropyl dithio phosphite, tin 〇, 〇- dipropyl dithiophosphate; dihydrocarbyl tin bis ( 0,0-bis-hydrocarbyl thiophosphates) such as monobutyltin bis (〇 '〇-bispropyl thiophosphate), and the like. Organotin compounds are better than inorganic tin compounds In the present invention, tetramethyltin is preferred. The term "dream" is used here to indicate the source of seconds, such as elemental sand, inorganic crushed compounds and organic crushed compounds, and any two or more of the above The mixture of anti-fouling agent described here is used for the treatment of the surface of the pyrolysis furnace pipeline. With this composition in contact with the surface of the cracking tube, this anti-fouling agent can be used in advance before filling the hydrocarbon feed. Treat the cracking tube, or add an effective amount of anti-scaling agent to the hydrocarbon feed to treat the cracking tube. Any piping method suitable for contacting the cracking furnace with the anti-scaling agent under suitable conditions can be used to provide the piping for processing The preferred method for pre-treating the cracking furnace piping includes filling the lining of the cracking furnace piping with a saturated or slightly overheated gas with a temperature ranging from about 3,000 to about 5,000T. When the pipeline is filled with gas, the cracking furnace should be burned to mention -10- this paper is applicable to the Chinese National Standard (CNS) A4 specification (21〇X297mm) (please read the precautions on the back before filling this page)
-IIP 經濟部中央標準局員工消費合作社印裂 A7 ----- B7 五、發明説明（8 ) 供過熱氣體，氣體自管路出來的溫度高於導入管路内襯的 氧體溫度。通常氣體流出物可具有高達約2 〇 〇 〇 的溫度。 因此處理溫度可爲從約3 Ο 〇 T至約2000T的範圍，較佳者 爲’從400 °F至1800 °F的範圍，且最佳者爲，從5〇〇 T至 1600 F的範圍。此溫度對於填充至裂解爐轉化部位的氣體 r 是適合的，因此首先送至轉化部位管路接著再送至放熱部 位管線。 然後抗垢劑可與被送入裂解管的氣體混合。可與氣體混 合的抗垢劑，爲純液體或抗垢劑與惰性稀釋劑的混合物。 在任何例子中，不論是純液體或是混合物，在導入或氣體 混合前’最好先汽化或是轉化成液化氣體。與氣體混合之 抗垢劑的量，可使抗垢劑在氣體中的濃度從約1 pprmn至約 10,000 ppmrn的範圍内，較佳者爲從約1〇 ppmm至約1000 ppmm 的範固内，且最佳者爲從20 ppmm至200 ppmm的範圍内。 氣體與抗垢劑的混合物，與裂解爐接觸或填充在裂解爐 ’需要一段時間’足以讓放置於裂解嚴的管路被處理，管 路可使得或促進煤焦剝落的量超過含矽抗垢劑所造成的量 。用來預先處理裂解管的時間，會受到包含管路的裂解爐 之特定位向所影響；但通常預先處理的時間可高達至約12 小時’若有需要還可更長。但較佳者，預先處理的時間在 從約0 . 1小時至約1 2小時的範圍間，最佳者，從〇 5小時至 1 0小時的範圍間。 在此例中’抗垢劑組成物直接與進料至裂解爐的烴類化 合物混合，其加入的量足以促進烴類進料熱裂解間產生的 -11- 本紙張尺度適用中國國ϋ準（CNS ) A4規格（2丨0 X297公釐） ~' (請先閱讀背面之注意事項再填寫本頁) 裝· 訂 經濟部中央標準局員工消費合作社印製 A7 ____B7 五、發明説明（9 ) ' '~~' 煤焦之剥落。由於來自抗垢劑使用的記憶效應，若必要， 與烴類裂解進料的混合物要間歇性地導入，但此對時間達 1 2小時以上者較佳。裂解爐管路處理時，在烴類裂解進料 中抗垢劑的濃度可從約1 ppmni至約1 〇,〇〇〇 ppmrtl的範圍内， 較佳者爲從約1 0 ppmm至約1000 ppmm的範園内，且最佳者 爲從2 0 ppmm至200 ppmm的範圍内。 ’ 關於圖1，顯示熱裂解方法系統的裂解爐部份1 〇之原理 表示。裂解爐部份10包含熱裂解裝置或裂解壚12，以提供 誘導烴類裂解所需的熱能。裂解爐丨2劃分爲對流區i 4和散 熱區16兩部份。在此區域中分別爲如管線18的對流線圏和 如管線2 0的散熱線圏。 烴類原科或氣體混合物，且將此烴類原料藉由線管22導 入對流管1 8的内襯内，線管2 2以流體流與對流管1 8互通。 裂解爐12的管路在處理時，氣體和抗垢劑組成物的混合物 ，可經由線管22導入對流管18。進料通過裂解爐12的管路 ’氣體在其中被加熱至裂解溫度以誘發裂解，或在管路進 行處理時，氣體被加熱至所需的處理溫度。從裂解爐12而 來的裂解產物氣體，經線管24送至分離器26，此爲一提供 裝置的區域，以去除至少一部份含在裂解產物氣流内的剝 落煤焦。從裂解產物氣流中去除的剝落煤焦，藉由線管2 8 送出分離器2 6，且在此除去具有至少部份剝落煤焦的裂解 產物氣體’藉由線管30送出分離器26。 爲提供操作裂解爐12所需的熱能，燃料氣體經線管32送 至裂解爐12的燃燒器34,藉燃燒氣體的燃燒使熱能釋放出 •12- (〇^)八4規格（210/ 297公慶） (請先閱讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標準局員工消費合作社印製 A7 ____B7 五、發明説明（10) 來。 處理對流管18和散熱管20時，抗垢劑组成物經線管36送 至裂解爐進料氣流，且在最終混合物送入裂解爐12前混合 。插在管線36的是熱交換器38，提供一熱交換裝置以傳遞 熱能，且藉此汽化進料轉化増強组成物。 < 下列的實例提供本發明更進一步的説明。 實例 下列兩個比較例説明，利用添加錫化合物而不加砂化合 物來促進煤焦的剝落。 一實驗用配備有HK4M合金管線的乙烯裂解爐，每小時進 料44 lb的乙缔，且在裂解時進料每小時13 2 1{5含3〇〇 ppmm硫的二甲硫，此爲目前裂解器的一般處理。轉化率保 持固定在6 5 %且滯留時間爲1 2 〇毫秒。刺落的煤焦在反應 器後的廢科區收集，在長達70小時的運轉可得每天4克。 相同的管路在塡充乙烷前，以100 ppmm的四丁基錫（不含矽 )處理6小時。在70小時運轉後，可收得的量爲每天14.5克 。在不同的運轉中，HK4 Μ管路在塡充乙烷前，以各爲 100 ppmm的四丁基錫和六甲基二矽氧烷處理6小時。在超 過100小時運轉後，煤焦收集速率在每天25克。以HK4M 管路做三次實驗性運轉的每一組數據都顯示在圖2。由此數 據分析可看出只以錫來處理，相較於以錫/碎或二甲基硫化 合物處理者，可得到明顯較大的煤焦剝落量。 一實驗用配備有HP改良合金管線的乙埽裂解爐，每小時 進料25_3 lb的乙晞，且在裂解時進料每小時76卟含300 -13· 本紙張尺度顧巾關家縣（CNS ) A4祕（2!0χ：!97/>ίΤ (請先閱讀背面之注意事項再填寫本頁) 訂 良-IIP Employee's Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 ----- B7 V. Description of the invention (8) Supply of superheated gas, the temperature of the gas coming out of the pipeline is higher than the temperature of the oxygen gas introduced into the pipeline lining. Generally the gas effluent may have a temperature of up to about 2,000. Therefore, the treatment temperature may range from about 300T to about 2000T, preferably from 400 ° F to 1800 ° F, and most preferably from 500T to 1600F. This temperature is suitable for the gas r filled to the conversion site of the cracking furnace, so it is first sent to the conversion site pipeline and then to the heat release section pipeline. The anti-fouling agent can then be mixed with the gas fed into the cracking tube. Anti-scaling agent that can be mixed with gas is pure liquid or a mixture of anti-scaling agent and inert diluent. In any case, whether it is a pure liquid or a mixture, it is best to vaporize or convert to liquefied gas before introduction or gas mixing. The amount of the anti-scaling agent mixed with the gas can make the concentration of the anti-scaling agent in the gas range from about 1 pprmn to about 10,000 ppmrn, preferably from about 10 ppmm to about 1000 ppmm, And the best is in the range from 20 ppmm to 200 ppmm. The mixture of gas and anti-fouling agent is in contact with the cracking furnace or filled in the cracking furnace. "It takes a period of time" enough to allow the pipeline placed in the cracking tank to be processed. The amount caused by the agent. The time used to pre-treat the cracking tube will be affected by the specific orientation of the cracking furnace that contains the pipeline; but usually the pre-processing time can be up to about 12 hours' or longer if necessary. However, preferably, the pre-treatment time is in the range of from about 0.1 hour to about 12 hours, and most preferably, in the range of from 0.5 hour to 10 hours. In this example, the anti-fouling agent composition is directly mixed with the hydrocarbon compound fed to the cracking furnace, and the amount added is sufficient to promote the generation of hydrocarbon feed during thermal cracking. CNS) A4 specification (2 丨 0 X297mm) ~ '(please read the precautions on the back before filling in this page) Binding · Order A7 ____B7 printed by Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs V. Invention description (9)' '~~' Peeling of coal char. Due to the memory effect from the use of anti-fouling agents, if necessary, the mixture with the hydrocarbon cracking feed should be introduced intermittently, but this is better for a time of more than 12 hours. During the treatment of the cracking furnace pipeline, the concentration of the antifouling agent in the hydrocarbon cracking feed may range from about 1 ppmni to about 10,000 ppmrtl, preferably from about 10 ppmm to about 1000 ppmm Within the range of 20 ppmm to 200 ppmm. With respect to Fig. 1, the principle representation of the cracking furnace part 10 of the thermal cracking method system is shown. The cracking furnace section 10 contains a thermal cracking device or cracker 12 to provide the thermal energy required to induce the cracking of hydrocarbons. The cracking furnace 丨 2 is divided into two parts: convection zone i 4 and heat dissipation zone 16. In this area are convection coils like line 18 and heat dissipation coils like line 20, respectively. Hydrocarbons or gas mixtures, and this hydrocarbon raw material is introduced into the lining of the convection pipe 18 through the line pipe 22, and the line pipe 22 communicates with the convection pipe 18 in fluid flow. When the pipeline of the cracking furnace 12 is processed, the mixture of the gas and the antiscalant composition can be introduced into the convection pipe 18 via the line pipe 22. The gas fed through the pipeline of the cracking furnace 12 is heated to the cracking temperature therein to induce cracking, or when the pipeline is processed, the gas is heated to the desired processing temperature. The cracked product gas from the cracking furnace 12 is sent to the separator 26 through the line pipe 24, which is an area for providing equipment to remove at least a part of the peeled coal char contained in the cracked product gas stream. The exfoliated coal char removed from the cracked product gas stream is sent out of the separator 26 through the line pipe 28, and here the removal of the cracked product gas having at least part of the exfoliated coal char is sent out of the separator 26 through the line pipe 30. In order to provide the heat energy required to operate the cracking furnace 12, the fuel gas is sent to the burner 34 of the cracking furnace 12 through the line pipe 32, and the combustion energy is used to release the heat energy to the 12- (〇 ^) 84 specification (210/297 Gongqing) (Please read the precautions on the back before filling in this page) Pack. Order A7 ____B7 printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (10). When treating the convection tube 18 and the heat dissipation tube 20, the anti-fouling agent composition is sent to the cracker furnace feed gas stream through the line pipe 36, and is mixed before the final mixture is sent to the cracker furnace 12. Inserted in line 36 is a heat exchanger 38, which provides a heat exchange device to transfer heat energy, and thereby vaporizes the feed to transform the strong composition. < The following examples provide a further explanation of the invention. Examples The following two comparative examples illustrate the use of tin compounds without sand compounds to promote the peeling of coal char. An ethylene cracking furnace equipped with an HK4M alloy pipeline was used for an experiment, and 44 lb of ethylene was fed per hour, and 13 2 1 {5 dimethyl sulfide containing 300 ppmm sulfur per hour was fed during the cracking. General handling of crackers. The conversion rate remained fixed at 65% and the residence time was 120 milliseconds. The scorched coal char is collected in the waste area behind the reactor, and can be obtained for 4 grams per day in a 70-hour operation. The same pipeline was treated with 100 ppmm of tetrabutyltin (without silicon) for 6 hours before filling with ethane. After 70 hours of operation, the recoverable amount is 14.5 grams per day. In different operations, the HK4 Μ pipeline was treated with tetrabutyltin and hexamethyldisilazane at 100 ppmm each for 6 hours before filling with ethane. After more than 100 hours of operation, the char collection rate was 25 grams per day. Each set of data for three experimental runs with HK4M pipeline is shown in Figure 2. From the data analysis, it can be seen that the treatment with tin alone can obtain a significantly larger amount of coal char peeling than the treatment with tin / crushed or dimethyl sulfide. An experimental pyrolysis furnace equipped with HP improved alloy pipeline, feeding 25_3 lb per hour of ethyl pyrolysis, and feeding 76 per hour during cracking containing 300 -13 · This paper standard Gujinguan County (CNS ) A4 Secret (2! 0χ:! 97 / > ίΤ (Please read the precautions on the back before filling out this page)
Sxll47 A7 B7 五、發明説明（„ ppmm硫的二子硫，此爲目前裂解器的一般處理。轉化率保 持固定在67%且滯留時間爲27〇毫秒。剝落的煤焦在反應 器後的廢料區收集，在長達55小時的運轉可得每天2克。 相同的i路在填充乙烷前，以1〇〇 的四丁基錫（不含矽 )處理6小時。在65小時運轉後，彳收得的量爲每天“克。 相較於硫處理運轉，增加12倍。在不同的運轉中，Hp改良 管路在心充乙烷前，以各爲1〇〇 的四丁基錫和四乙基 碎燒處理6小時。在超過3天料轉後，職收集速率在每 天2克。三次實驗性運轉的每_組數據都顯示在圖3。由此 數據分析可看出只以锡來處理，相較於以锡/♦或二甲基硫 化合物處理者，可得到明顯較大的煤焦剝落量。Sxll47 A7 B7 Fifth, the invention description ("ppmm sulfur disulfide, this is the general treatment of the current cracker. The conversion rate remains fixed at 67% and the residence time is 27O milliseconds. The exfoliated coal char is in the waste area behind the reactor Collected, you can get 2 grams per day for up to 55 hours of operation. The same i-way is treated with 100% tetrabutyltin (without silicon) for 6 hours before being filled with ethane. After 65 hours of operation, it is collected The amount is "g" per day. Compared with the sulfur treatment operation, it is increased by 12 times. In different operations, the Hp modified pipeline is treated with 100% tetrabutyltin and tetraethyl each before being charged with ethane. 6 hours. After more than 3 days of transfer, the collection rate is 2 grams per day. The data for each group of the three experimental runs is shown in Figure 3. From this data analysis, it can be seen that only tin is processed, compared to Those treated with tin / ♦ or dimethyl sulfide can get a significantly larger amount of coal char peeling.