1317376 玖、發明說明： 發明所屬之技術領域 本發明係有關一種將廢塑膠熱裂解液化以生產油的方 法0 先前技術 廢塑膠熱裂解液化產油程序是廢塑膠有效回收利用的 _ 程序之一。但廢塑膠中聚乙烯（包括高密度與低密度兩者） 所佔的比率相當的高，其在熱裂解液化時易有蠟的產生。 一般處理程序是將裂解物分兩段冷卻，第一段使液態油躐 與氣體成份分離，第二段再將油蠛繼續冷卻，使固態躐與 液態油分離，然後再將固態蠟與原料混合後再次裂解。此 程序之缺點有：（一）、蠟完全冷卻至固態再行裂解，能源 效率較差。（二）、易有管路堵塞的情形發生。 若要線上一次即讓蠟的比率降低至可接受的程度（不 • 造成後續處理的困擾），則必須提高裂解溫度或裂解時間， 前者將使得產物中氣體比率昇高，產油率降低，後者除將 降低處理速率外，亦會有產物中氣體比率昇高的情形。 韓國專利KR9613605是有關一種將廢塑膠熱裂解液化 以生產油的技藝，其中將高沸點成份（即類壤部分）與低沸 點f份（即類油部分）同時冷凝於—收集槽内，然後才將底 部高沸點成份迴送加熱再裂解。 發明内容 5 1317376 、田本發明的主I目的在於提供一種如何在不冑高熱裂解 溫度，或大幅延長熱裂解時間的情況下，而於線上一次即 讓躐的比率降低至可接受的程度，而達到提高廢塑朦熱裂 解液化產油處理方法的產油率。 本發明的蠟即時迴流再裂解式廢塑膠熱裂解液化產油 方法（為一常壓式—即非加壓式一連續式處理程序）與一般 處理程序相較，多了一氣態冷卻截留器，以冷卻並攔截熱 • 裂解所產生的氣態頂部產品中的氣態蠟（常溫下之狀態為 壤）’使之成為高溫液體’而迴流至熱裂解反應器繼續裂 解’但其中的氣態油（常溫下之狀態為油）與氣體仍保持氣 態離開該截留器，再以冷卻器冷凝收集為成品油。如此， 則可在不提高熱裂解溫度，或大幅延長熱裂解時間的情況 下’於線上即讓蝶的比率降低至可接受的程度，並達到提 馬廢塑膠熱裂解液化產油的產率的目的。此外，蠟不必完 全冷卻至固態再行回收裂解，能源效率較佳，亦不會有管 # 路堵塞的情形發生。本發明與前述韓國專利KR9613605不 同之特點為：本發明方法中低沸點成份（油）並不與高沸點 成份（躐）同時冷凝’而是僅將高沸點成份（蠟）冷凝迴流再裂 解’其迴流溫度較高，較具經濟效益。 實施方式 本發明提供一種廢塑膠熱裂解液化產油方法，包含下 列步驟： a)熱裂解一廢塑膠而產生一氣態碳氫物質； 1317376 b) 冷部截留該氣態碳氫物質中於常溫下為蠟的氣態蠟 4份，使該氣態蠟部份成為液體並迴流至步驟a)再裂解； 及 ， c) 冷部從步驟b)出來的該氣態碳氫物質被截留氣態蠟 部份的殘餘部份，而獲得一常溫下為液態的液態油產品。 較佳的，步驟b)的液體的迴流係藉由重力而達成。 較佳的，步驟b)的冷卻截留係於一填充塔中進行，於 #是避免因為步驟a)的氣態碳氫物質的流量太大導致步驟b) 的液體無法迴流的情形。更佳的，該填充塔的溫度藉由也 -冷卻流體進行熱交換而被維持在一預定的溫度範圍，： 如該冷卻流體係流過設於該填充塔的外壁的襯套及/設於 該填充塔内部的一冷卻蛇管或套管而進行該熱交換。 較佳的，步驟a)的熱裂解係於一流體化床反應器及通 人-惰性氣體於該流體化床反應器底部的情形下進行。更 佳的，該流體化床反應器被維持於45〇_7〇〇〇c及該惰性氣 鲁體為氮氣。 較佳的，當該流體化床反應器被維持於45〇 7〇〇<^的 溫度時，該填充塔被維持於比該流體化床反應器低 195-410°C 的溫度。 本發明方法的一較佳具體實施例將配合圖i說明如 下。廢塑膠或廢有機物卜計量螺桿進料機ig的料斗u 被導入於該進料機的進料螺桿12。通過該進料螺桿η的 轉動及包覆於該螺桿12的電熱失套（未示於圖中），該廢塑 膠或廢有機物被破碎及至少部份位s 丨伪熔嘁，並由該螺桿12的出 1317376 料端直接進入一氣泡式流體化床熱裂解反應器2〇。 躁汉應 器20被維持在使該廢塑膠或廢有機物裂解產生氣態碳氯 物質的反應溫度’並且其底部被導入一以預熱器6 ”UVJ頂无加 熱之熱氮氣（NO來提供該反應器20内熱裂解物質的流體化 動力及氣泡的產生。如果情況需要，該熱氮氣亦可供應至 該進料斗11的底部（如虛線所示）以幫助進料。氮氣的供應 由一氮氣貯槽70及一壓縮機8〇來達成。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for thermally liquefying waste plastics to produce oil. 0 Prior Art The waste plastic thermal cracking liquefaction production procedure is one of the procedures for efficient recycling of waste plastics. However, the ratio of polyethylene (both high density and low density) in waste plastics is quite high, and it is easy to produce wax during thermal cracking liquefaction. The general treatment procedure is to separate the lysate in two stages. The first stage separates the liquid oil from the gas component, the second stage continues to cool the oil, separates the solid mash from the liquid oil, and then mixes the solid wax with the raw material. After cleavage again. The disadvantages of this procedure are: (1) The wax is completely cooled to solid state and then cracked, and the energy efficiency is poor. (2) It is easy to have a pipeline blockage. To reduce the wax ratio to an acceptable level once on the line (not causing subsequent processing problems), the cracking temperature or cracking time must be increased, the former will increase the gas ratio in the product, and the oil yield will decrease. In addition to lowering the processing rate, there will also be cases where the gas ratio in the product is increased. Korean patent KR9613605 is a technique for liquefying waste plastics to produce oil, in which high-boiling components (ie, soil-like parts) and low-boiling point f (ie, oil-like parts) are simultaneously condensed in a collecting tank, and then The bottom high boiling component is returned to heat and lysed. SUMMARY OF THE INVENTION 5 1317376, The main purpose of the invention is to provide a way to reduce the rate of enthalpy to an acceptable level once on the line without high pyrolysis temperature, or to greatly extend the thermal cracking time. The oil production rate of the waste plastics pyrolysis liquefied oil production method is improved. The instant reflow-reversing waste plastic thermal cracking liquefaction oil production method of the invention (for a normal pressure type, that is, a non-pressurized one continuous treatment program) has a gas cooling trap, compared with a general treatment program. Cooling and intercepting the gaseous wax in the gaseous top product produced by heat cracking (the state at room temperature is soil) 'make it a high temperature liquid' and return to the thermal cracking reactor to continue cracking 'but the gaseous oil (at room temperature) The state is oil) and the gas remains in a gaseous state leaving the trap, and then condensed by a cooler to collect the product oil. In this way, the ratio of the butterfly can be reduced to an acceptable level on the line without increasing the thermal cracking temperature or greatly prolonging the thermal cracking time, and the yield of the thermal decomposition liquefied oil of the Tama waste plastic can be achieved. purpose. In addition, the wax does not have to be completely cooled to the solid state for recycling and cracking, and the energy efficiency is better, and there is no tube blockage. The difference between the present invention and the aforementioned Korean patent KR9613605 is that the low-boiling component (oil) in the method of the invention does not condense simultaneously with the high-boiling component (躐), but only the high-boiling component (wax) is condensed and refluxed and then cracked. The reflux temperature is higher and more economical. Embodiments The present invention provides a waste plastic thermal cracking liquefaction oil production method comprising the following steps: a) thermally cracking a waste plastic to produce a gaseous hydrocarbon substance; 1317376 b) the cold portion intercepts the gaseous hydrocarbon material at room temperature 4 parts of the gaseous wax of the wax, the part of the gaseous wax is made into a liquid and refluxed to the step a) to be further lysed; and, c) the gaseous hydrocarbon material from the step b) is trapped in the residual portion of the gaseous wax portion A liquid oil product that is liquid at room temperature is obtained. Preferably, the reflux of the liquid of step b) is achieved by gravity. Preferably, the cooling entrapment of step b) is carried out in a packed column, in order to avoid the situation in which the liquid of step b) cannot be returned due to the large flow of gaseous hydrocarbon species in step a). More preferably, the temperature of the packed column is maintained at a predetermined temperature range by heat exchange of the cooling fluid: if the cooling flow system flows through the liner provided on the outer wall of the packed column and/or The heat exchange is performed by a cooling coil or sleeve inside the packed column. Preferably, the thermal cracking of step a) is carried out in the case of a fluidized bed reactor and a pass-inert gas at the bottom of the fluidized bed reactor. More preferably, the fluidized bed reactor is maintained at 45 〇 7 〇〇〇 c and the inert gas is nitrogen. Preferably, when the fluidized bed reactor is maintained at a temperature of 45 Torr, the packed column is maintained at a temperature 195-410 ° C lower than the fluidized bed reactor. A preferred embodiment of the method of the present invention will be described below in conjunction with Figure i. The hopper u of the waste plastic or waste organic material metering screw feeder ig is introduced into the feed screw 12 of the feeder. Through the rotation of the feed screw η and the electric heating sleeve (not shown) coated on the screw 12, the waste plastic or waste organic matter is broken and at least partially s 丨 丨 嘁 嘁 嘁12 out of the 1317376 material end directly into a bubble fluidized bed thermal cracking reactor 2〇. The 应汉应20 is maintained at a reaction temperature that causes the waste plastic or waste organic matter to be cracked to produce a gaseous carbon and chlorine substance, and the bottom portion thereof is introduced into a preheater 6 "UVJ top without heating hot nitrogen (NO to provide the reaction) The fluidization power of the pyrolysis material in the vessel 20 and the generation of bubbles. If necessary, the hot nitrogen gas may also be supplied to the bottom of the feed hopper 11 (as indicated by the dashed line) to aid in the feed. The supply of nitrogen is supplied by a nitrogen storage tank. 70 and a compressor 8 to achieve.
於該反應器20内因熱裂解所產生的氣態碳氫物質頂 部產品由其上部通過一管路被導出錢入一 4態織冷卻截 留器3〇，於是常溫下為蠘之氣態蠛在截留器30内被冷卻 成為高溫液體並迴流至該反應器2G内繼續進行裂解。同時 未被冷卻的氣態物質則由該截留器3〇的頂部通過一管路 44㈣出並進人—油冷凝器4()。由於熱裂解所產生的氣態 碳氫物質頂部產品内的氣態蠟(常溫下為蠟)已被截留並以 液態方式迴流至該反應器20，因此從該截留器30頂部流 出的氣態物質不會在管路44内形成固態蠟，而避免了管路 堵塞的問題。同理，访„ §" 7凝器40冷卻由該截留器30出 來的乱態物質的產物將為 ^ ^ 將為液態油（收集於—貯油槽50内）及 未冷凝的油氣（由管路45 排出至下游處理單元），也不會有 固態蠟堵塞其中的問題。 ）也不會有 適用於本發明的氣態蝶冷卻截留 施例如圖2及3所 "佳，、體實 於導入該碳氫物質頂部產、槽體31，位於該槽體底端用 a ^ A . .. °〇的入口 32，位於該槽體頂端 用於導出未被冷卻的氣態物質的一出口⑽，及介於Η線 1317376 與B-B線之間的冷卻截留段34。該冷卻截留段包含一内冷 卻套管35，一設於該槽體之槽壁36上的外冷卻襯套37， 被填充於該内冷卻套管與該槽壁之間的填充物38(例如拉 西環），及支撐該填充物的支撐網39。該内冷卻套管35具 有一夾層通道351，冷卻流體（未示於圖中）由該夾層通道 351的上方流入而由其下方流出。該外冷卻襯套37與該槽 壁36之間亦具有一夾層通道361，冷卻流體（未示於圖中） φ 由該夾層通道361的上方流入而由其下方流出。藉由該填 充物所提供的碰撞攔截的作用及兼具冷卻介質作用；配合 該夾層通道351、361内的冷卻流體的控制將填充物38 /氣 態頂部產品的降溫至適當溫度來使氣態碳氫物質頂部產品 内的氣態蠟被截留並以液態方式迴流至該反應器2〇。 視廢塑膠熱裂解液化產油的規模，該氣態蠟冷卻截留 器30的該内冷卻套管犯及該槽壁％之直徑可被調整，也 可增加該内冷卻套管35的數目而具有多個冷卻流體迴路及 • 多個被填充的環形通道。 對照例 在“、、前述本發明方法所使用的氣態蠟冷卻截留器 應用時’氣泡式流體化床熱裂解低密度聚乙稀塑膠 iLDPE)時之效果如表—所示，其中熱裂解反應溫度為500 c~550°c時，產油率介於43.2〜43·9%，躐的產率達 1317376 表一低密度聚乙烯於流體化床熱裂解之產物與熱裂解溫度關係(wt.%)* 產物 溫度(°C) 500 550 600 650 700 氣體 10.8 21.4 24.2 40.1 71.4 油 43.9 43.2 51.0 47.8 24.6 蠟 45.3 35.4 24.8 12.1 4.0 油+蠛 89.2 78.6 75.8 59.9 28.6 * 資料來源：“Fluidised bed pyrolysis of low density polyethylene to produce petrochemical feedstock55 Paul T. Williams, Elizabeth A. Williams Journal of Analytical and Applied Pyrolysis 51 (1999) 107-126 實施例 於對照例的氣泡式流體化床熱裂解反應器後接上圖2 及3所示的氣態蠟冷卻截留器3〇後’氣泡式流體化床熱裂 解低密度聚乙烯塑膠（LDPE)之改善效果如表二所示，其中 熱裂解反應溫度於515。(：~530。(：時（氣態蠟冷卻截留器3〇9 上端的溫度為120〜320。〇,產油率介於55·3~59 4%，比無 氣態蠟冷卻截留器時之43.2〜43.9%高31.7%，蠟的產率低 於7.0/.3%比無氣態蠛冷卻截留器時之35.㈠5 3%相較低 了許多，I至比表-中的無氣態纖冷卻截留器、反應溫度 高達罐。c時之產油率51.G%及產壤率24 8%的效果更佳。 本發明壤即時迴流再裂解式廢塑膠熱裂解液化產油方 1317376 法於氣態蠟冷卻截留器配合使用下，於氣泡式流體化床熱 裂解低密度聚乙烯塑膠（LDPE)時，可實際達到攔截蠟迴流 再裂解之效果。 表二環狀式氣態蠟冷卻截留器配合氣泡式流體化床裂解低密度聚乙烯塑 膠(LDPE)時裂解產油率(wt.%) 產物 裂解溫度(°C) 515〇C 530〇C 氣體 37.7 32.3 油 55.3 59.4 蠟+其他 7.0 8.3 圖式簡單說明 圖1顯示本發明方法的一較佳具體實施例的示意流程 圖。 圖2顯示適用於本發明方法的一氣態冷卻截留器的示 意剖視圖。 圖3顯示介於圖2中的A-A與B-B線之間的氣態冷卻 截留器的冷卻截留段34的示意立體圖。 主要元件之圖號說明 10..進料機；11..料斗；12..進料螺桿；20.·反應器； 30·.截留器；40..油冷凝器；44、45..管路；60..預熱器； 70.. 氮氣貯槽；80..壓縮機；31..槽體；32..入口； 33..出口； 34.. 冷卻截留段；35.·内冷卻套管；36._槽壁；37..外冷卻襯 11 1317376 套；38.·填充物；39..支撐網；351、361..夾層通道 、 9The top product of the gaseous hydrocarbon material generated by the thermal cracking in the reactor 20 is led out from the upper portion through a pipeline into a 4-state woven cooling trap 3〇, so that the gaseous state of the crucible is at the trap 30 at normal temperature. The inside was cooled to a high temperature liquid and refluxed into the reactor 2G to continue the cracking. At the same time, the uncooled gaseous material exits the top of the trap 3 through a line 44 (d) and enters the human-oil condenser 4 (). Since the gaseous wax (wax at normal temperature) in the top product of the gaseous hydrocarbon substance produced by the thermal cracking has been trapped and returned to the reactor 20 in a liquid state, the gaseous substance flowing out from the top of the trap 30 does not Solid wax is formed in the line 44 to avoid the problem of blockage of the line. Similarly, the visit of the § " 7 condenser 40 to cool the product of the disordered material coming out of the trap 30 will be liquid oil (collected in the sump 50) and uncondensed oil and gas (by the tube) The road 45 is discharged to the downstream processing unit), and there is no problem that the solid wax is blocked.) There is no gas butterfly cooling intercepting device suitable for the present invention, for example, as shown in Figs. 2 and 3, The hydrocarbon material is produced at the top of the tank, and the tank body 31 is located at the bottom end of the tank body with an inlet 32 of a ^ A . . . , at the top of the tank body for guiding an outlet (10) of the uncooled gaseous substance, and a cooling intercepting section 34 between the twist line 1317376 and the BB line. The cooling cut-off section includes an inner cooling sleeve 35, and an outer cooling bushing 37 disposed on the groove wall 36 of the tank body is filled in the a filler 38 (for example, a Raschig ring) between the inner cooling sleeve and the groove wall, and a support net 39 supporting the filler. The inner cooling sleeve 35 has a sandwich channel 351 for cooling fluid (not shown) Middle) flows in from above the sandwich channel 351 and flows out from below. The outer cooling bushing 37 is The slot wall 36 also has a sandwich channel 361 between which a cooling fluid (not shown) φ flows from above the sandwich channel 361 and flows downwardly therefrom. The impact of the collision is provided by the filler and The combination of the cooling medium and the cooling fluid in the sandwich channels 351, 361 cools the filler 38 / gaseous top product to a suitable temperature to trap the gaseous wax in the gaseous hydrocarbon head product and liquid Reflux to the reactor 2〇. Depending on the scale of the waste plastic thermal cracking liquefied oil production, the inner cooling jacket of the gaseous wax cooling trap 30 may be adjusted to the diameter of the groove wall, and the internal cooling may be increased. The number of sleeves 35 has a plurality of cooling fluid circuits and a plurality of filled annular passages. The comparative example is in the case of "the gaseous wax cooling trap used in the foregoing method of the present invention" bubble fluidized bed thermal cracking. The effect of low-density polyethylene plastic iLDPE) is shown in Table--When the thermal cracking reaction temperature is 500 c~550 °c, the oil production rate is between 43.2 and 43.9%, and the yield of rhodium is 1317376. One Relationship between product of thermal decomposition of density polyethylene in fluidized bed and thermal cracking temperature (wt.%)* Product temperature (°C) 500 550 600 650 700 Gas 10.8 21.4 24.2 40.1 71.4 Oil 43.9 43.2 51.0 47.8 24.6 Wax 45.3 35.4 24.8 12.1 4.0 Oil + 蠛 89.2 78.6 75.8 59.9 28.6 * Source: "Fluidised bed pyrolysis of low density polyethylene to produce petrochemical feedstock55 Paul T. Williams, Elizabeth A. Williams Journal of Analytical and Applied Pyrolysis 51 (1999) 107-126 The bubble fluidized bed thermal cracking reactor of the comparative example is followed by the gaseous wax cooling trap 3 shown in Figures 2 and 3, and the effect of the bubble fluidized bed thermal cracking low density polyethylene plastic (LDPE) is as follows. Table 2 shows the thermal cracking reaction temperature at 515. (:~530.(:: (The temperature of the upper end of the gas-wax cooling trap 3〇9 is 120~320. 〇, the oil production rate is between 55·3~59 4%, 43.2 compared with the non-gaseous wax cooling trap) ~43.9% high 31.7%, the wax yield is lower than 7.0/.3% than when there is no gas enthalpy cooling trap 35. (a) 5 3% phase is much lower, I to the table - in the air-free fiber cooling interception The reaction temperature is as high as that of the tank. The oil production rate of 51. G% and the soil yield of 24% are better. The present invention is a real-time reflux re-degradable waste plastic thermal cracking liquefaction oil production party 1317376 method of gaseous wax When the cooling trap is used together, when the bubble fluidized bed is thermally cracked low-density polyethylene plastic (LDPE), the effect of intercepting the wax backflow and re-cracking can be achieved. Table 2 Annular gaseous wax cooling trap with bubble fluid Cracking oil production rate (wt.%) when the bed is cracked low density polyethylene plastic (LDPE) Product cracking temperature (°C) 515〇C 530〇C gas 37.7 32.3 oil 55.3 59.4 wax + other 7.0 8.3 simple illustration 1 shows a schematic flow chart of a preferred embodiment of the method of the invention. Figure 2 shows a suitable embodiment of the invention. A schematic cross-sectional view of a gaseous cooling trap. Figure 3 shows a schematic perspective view of the cooling trap 34 of the gaseous cooling trap between line AA and line BB in Figure 2. Description of the major components Figure 10. Feeding 11.11.. Hopper; 12.. Feed screw; 20. Reactor; 30.. Interceptor; 40. Oil condenser; 44, 45.. Pipe; 60.. Preheater; Nitrogen storage tank; 80.. compressor; 31. tank; 32.. inlet; 33.. outlet; 34.. cooling interception section; 35. internal cooling casing; 36._ groove wall; Outer cooling lining 11 1317376 sets; 38.·filling; 39.. support net; 351, 361.. mezzanine channel, 9
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