TW565468B - Method and device for recovering hydrocarbon vapor - Google Patents

Abstract

The present invention relates to a method and a device for recovering hydrocarbon vapor contained in air or other gases escaped rom liquid hydrocarbon, such as gasoline, stored in a storage facility, such as a storage cylinder, due to thermal expansion. The method of recovering hydrocarbon vapor comprising a first step of cooling a gas containing hydrocarbon vapor by a first heat exchanger (11) to condense the same and removing part of the hydrocarbon vapor, a second step of heating the gas, which has part of its hydrocarbon vapor removed therefrom, by a second heat exchanger (14) to raise its temperature, and a third step of feeding the temperature-raised gas to adsorption towers (15, 16) filled with an adsorbent, where the hydrocarbon vapor is adsorbed for removal. Separation of the hydrocarbon from the adsorbent is effected by reducing the pressures in the adsorption towers (15, 16) while producing a counterflow of clean gas in the adsorption towers (15, 16).

Description

565468 A7 B7 五、發明說明（1 ) 技術領域 本發明係關於回收被含於在儲存筒等之儲存設備塡充 汽油等之液狀碳氫化合物之際，或由於氣溫而膨脹，由該 儲存設備被排出之空氣、其它之氣體之碳氫化合物蒸氣之 方法及裝置。 經濟部智慧財產局員工消費合作社印製 背景技術 將汽油、燈油、輕油等液狀碳 船、卡車、儲存筒之際，由於這些 置換，或位於容器內之空氣等之氣 脹，由該容器被排出含有碳氫化合 合物之一部份成分揮發所產生之蒸 中之碳氫化合物蒸氣之濃度，在夏 最近，關於此碳氫化合物蒸氣 範。例如，在依據都道府縣之公害 濃度爲5〜8%，去除率爲8 0〜 污染大氣物質中，設有更嚴格之限 先前由儲存筒來之排氣氣體中 收方法，有如下者被提案。 ①使用塡充活性碳之去除裝置 後，藉由加熱蒸氣以分離吸著後之 利用塡充氧化矽膠或沸石之去除裝 氣後，藉由減壓以分離吸著後之碳 分離方法。 氫化合物塡 容器內之氣 體因應氣溫 物之蒸氣（ 氣）之氣體 天會達到3 之排出，已 防止條例等 9 0 %。而 制。 之碳氫化合 充於平底貨 相與液相之 之變化而膨 液狀碳氫化 。此種排氣 0 %。 經有限制規 之限制中， 且，在有害 物蒸氣之回 請 先 閱 讀 背 & 之· 注 意 事 項 再 填 本 頁 ’吸者碳氣化合物蒸氣 碳氫化合物之方法，② 置以吸著碳氫化合物蒸 氫化合物之方法，③膜 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4- 565468 A7 ___ B7 五、發明說明（2 ) 另一方面’爲了改善上述習知之碳氫化合物蒸氣之回 收方法之回收效率，被提案如下之發明（特開平1 ◦一 1 5 6 1 2 7號公報）。 在此發明中，於回收塔中，使含有高濃度苯之排出氣 體與預冷之重油或苯接觸’ 一部份去除苯蒸氣後，於被塡 充吸著劑之吸著塔吸著去除苯蒸氣。由吸著劑分離苯之際 ’將吸著塔一邊以內部流過蒸氣之加熱盤管等加熱，一邊 以真空泵等減壓進行之。分離之苯返回上述回收塔，被凝 縮回收。 依據本發明，一部份回收苯蒸氣後，在吸著塔吸著之 故，可以接近極限地去除苯，分離之苯之後處理也容易。 但是，由吸著劑分離苯之際，以流過蒸氣之加熱盤管 等加熱吸著塔，此間接加熱方式效率不好。而且，氧化矽 膠等之吸著劑熱傳導度低之外，粒狀體間之接觸爲點接觸 之故，吸著劑塡充層之傳熱非常之慢。 經濟部智慧財產局員工消費合作社印製 又，在通常之壓力·溫度擺動吸著（PTSA : Pressure & Temperature Swing Absorption )中，吸著·分 離之切換以數分鐘之程度進行，在此程度之時間中，實質 上只在加熱盤管之表面附近數c m之距離會升溫。因此， 有必要很多加熱盤管，吸著塔之空間變成需要多，在吸著 劑層會產生溫度不均，加熱用蒸氣之損失變多。 發明之公開揭露 本發明之目的在於提供··由含有碳氫化合物蒸氣劑之 -5- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 合 經濟部智慧財產局員工消費合作社印製 565468 A7 B7 五、發明說明（3 ) 氣體可以有效率地回收碳氫化合物蒸氣之碳氫化合物蒸氣 之回收方法及其裝置。 本發明之碳氫化合物蒸氣之回收方法之特徵爲具有： 藉由冷卻手段，冷卻凝縮含有碳氫化合物蒸氣之氣體，以 去除上述碳氫化合物蒸氣之一部份之第1工程，及藉由加 熱手段以加熱上述碳氫化合物蒸氣之一部份被去除之氣體 ，以提升溫度之第2工程，以及將上述升溫之氣體供給於 被塡充吸著劑之吸著手段，在此，吸著去除上述碳氫化合 物蒸氣之第3工程。 在第1工程處理後之氣體之溫度超過含有成分之凝固 點，而且，處理成此凝固點附近之低的溫度。 此溫度使之愈低溫’縮重愈增加，氣體中之碳氣化 物蒸氣之濃度減少，因此，後段之負荷變小，可以使吸 著手段之吸著塔小。例如，在苯成爲碳氫化合物蒸氣之主 成分之情形’本之凝固點爲5 · 5 C之故，最好爲6〜 2〇°C，更理想爲6〜1 0 °C。 藉由此種之第1工程，例如被含於藉由石炭之乾餾所 產生之以苯爲主成分之粗輕油等之甲苯、二甲苯、三甲苯 、香豆酮、茚（indene )等之高沸點不純物，特別是昇華性 固體之萘（naphthalene)藉由冷卻之蒸氣壓降低與對苯之 溶解，可以有效地被去除。 在第2工程加熱後之氣體之溫度，最好加熱爲比在先 前之第1工程處理後之溫度高5〜3 0 °C之溫度。更好爲 高1〇〜2〇°C之溫度。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -6 - 請 先 閱 讀 背 面 之 注 意 事 項 頁 565468 A7 B7 五、發明.說明（4 ) 設爲此種溫度原因在於：在第1工程之處理中，碳氫 化合物蒸氣達到冷卻時之溫度之飽和狀態之故’於配管途 中或吸著塔中，又，在冬季之散熱等，溫度更爲降低之情 形，會引起即刻凝縮或固體析出。此現象會引起配管之阻 塞、切換閥之動作不良或吸著塔之壓力損失之上升。 相對於此，藉由第2工程，可以使第1工程後之氣體 升溫，降低碳氫化合物蒸氣之飽和度，可以使之不易引起 在配管等之凝縮。又，提升後段之吸著裝置之溫度，可以 使吸著後之分離再生容易。進而，藉由使碳氫化合物蒸氣 之濃度降低，接著之第3工程之負荷減少，可以使吸著塔 或真空泵小型化。 經濟部智慧財產局員工消費合作社印製 另一方面，接著之第3工程之吸著塔內之吸著劑藉由 碳氫化合物蒸氣之吸著，溫度上升，藉由分離溫度下降。 吸著量爲數％之情形，溫度之偏差爲數°C。因此，不進行 第2工程之加熱升溫操作，由吸著劑之碳氫化合物蒸氣之 分離操作終了後丨吸著劑之溫度下降時，如導入包含飽和 濃度之碳氫化合物蒸氣之氣體，可能會引起在吸著塔之入 口凝縮、固體析出。反之，導入氣體之溫度如過高，吸著 容量減少之故，吸著效率降低。 被塡充於第3工程之吸著手段之吸著劑，可以使用氧 化矽膠、沸石、氧化鋁凝膠、活性碳等之一般的吸著劑。 由安全性之觀點，最好使用氧化矽膠、沸石、氧化鋁凝膠 0 更理想爲被高溫熟成或以疏水處理劑處理之氧化矽膠 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565468 A7 B7 五、發明說明（5 ) 、或矽/氧化鋁比爲8 0以上之高矽沸石。吸著劑如吸收 氣體中之水分，由回收油之水的分離作業成爲必要之故， 以雖不易吸著水分，但是吸著碳氫化合物之所謂的疏水性 之吸著劑較爲理想。 上述所謂之吸著手段例如爲吸著塔。 於此種第3工程中，藉由吸著劑，碳氫化合物蒸氣被 吸著去除，被排出淸淨之氣體。 又，於第3工程中，吸著碳氫化合物類之吸著劑藉由 減壓，碳氫化合物類被分離而被再生。分離時之真空度最 好在絕對壓力6 Ο T 〇 r r以下。更好爲絕對壓力2 5 T 〇 r r以下。絕對壓力愈低，碳氫化合物蒸氣愈容易分 離。吸著劑如碳氫化合物類之分離不充分，於下一次之吸 著操作時，碳氫化合物蒸氣變得不易吸著，碳氫化合物蒸 氣之去除效率降低。 經濟部智慧財產局員工消費合作社印製 另一方面，由吸著劑被分離之碳氫化合物蒸氣成爲非 常高之濃度，藉由冷卻，容易凝縮成爲液體被回收。冷卻 方法一般可以使用熱交換器（管式、板式等）。又，無法 凝縮之低濃度碳氫化合物蒸氣藉由混合於裝置入口之原料 氣體，可以不排除於裝置外地處理之。 碳氫化合物蒸氣之其它的回收方法也可以與冷卻輕油 、燈油、汽油、回收油等接觸，使之冷卻凝縮，或使之溶 解其中以回收之。又，無法凝縮或溶解之低濃度碳氫化合 物蒸氣也可以與上述相同地，混合於裝置入口之原料氣體 -8- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565468 A7 B7 五、發明說明（6 ) 再者，也可以將分離之碳氫化合物蒸氣與含有第1工 程之碳氫化合物蒸氣之氣體混合，使之冷卻凝縮以加以回 收。 又，回收碳氫化合物蒸氣之對象氣體通常之空氣外， 類似氮氣、其它之惰性氣體等之氣體也可以，可以適當適 用於由碳氫化合物蒸氣之發生源之液化碳氫化合物之製造 或儲存設備等被排出之各種氣體等。 本發明之回收方法中，期望在第1工程，使用上述凝 縮之液狀的碳氫化合物，使冷卻之此液狀的碳氫化合物與 含有碳氫化合物蒸氣之氣體接觸，以冷卻凝縮氣體中之碳 氫化合物蒸氣。 如此爲之，使用上述凝縮之液狀之碳氫化合物之故， 可以有效率地回收。565468 A7 B7 V. Description of the Invention (1) Technical Field The present invention relates to the recovery of liquid hydrocarbons contained in storage equipment such as storage cylinders filled with gasoline and the like, or expanded due to air temperature. Method and device for exhausting hydrocarbon vapor of air and other gases. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economics. BACKGROUND OF THE INVENTION When liquid carbon vessels such as gasoline, kerosene, light oil, etc. The concentration of the hydrocarbon vapor in the steam produced by the volatilization of a part of the components containing the hydrocarbon compound was vaporized recently. For example, according to the prefectures, the pollution concentration is 5 ~ 8%, and the removal rate is 80 ~. Among the polluted air substances, there is a stricter method for collecting the exhaust gas from the storage cylinder. Was proposed. ① After using an activated carbon-filled carbon removal device, the adsorbed carbon is separated by heating the steam to remove the adsorbed carbon. The oxygen-filled silica or zeolite is removed and the pressure is reduced to separate the adsorbed carbon. Hydrogen compounds 之 The gas in the container will be discharged in accordance with the temperature of the vapor (gas) of the gas. The gas will be discharged in 3 days, and 90% of the regulations have been prevented. While system. The hydrocarbon is filled with the change of the liquid phase and the liquid phase of the flat bottom to expand the liquid hydrocarbon. This exhaust is 0%. Subject to restrictions, and please read back & precautions before returning the vapor of harmful substances, and then fill in this page 'Method of inhaling carbon gas vapor hydrocarbon, ② Place it to absorb hydrocarbons The method of steaming hydrogen compounds. ③ The size of the paper is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -4- 565468 A7 ___ B7. 5. Description of the invention (2) On the other hand, in order to improve the above The recovery efficiency of the hydrocarbon vapor recovery method has been proposed as the following invention (Japanese Patent Application Laid-Open No. 1 ◦-1 5 6 1 2 7). In this invention, in the recovery tower, the exhaust gas containing a high concentration of benzene is brought into contact with pre-cooled heavy oil or benzene. After partially removing benzene vapor, the benzene is adsorbed and removed in an adsorption tower filled with an adsorbent. Steam. When benzene is separated by a sorbent ′ The absorbing tower is heated by heating coils or the like through which steam flows inside, and is depressurized by a vacuum pump or the like. The separated benzene is returned to the recovery column and recovered by condensation. According to the present invention, after a part of the benzene vapor is recovered, the benzene can be adsorbed in the adsorption tower, and the benzene can be removed to the limit, and the separated benzene can be easily processed afterwards. However, when the benzene is separated by the sorbent, the indirect heating method is not efficient because the absorption tower is heated by a heating coil or the like through which steam is passed. Moreover, in addition to the low thermal conductivity of sorbents such as silica gel, the contact between the granular bodies is point contact, and the heat transfer of the sorbent filling layer is very slow. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In normal pressure and temperature swing absorption (PTSA: Pressure & Temperature Swing Absorption), the switch between adsorption and separation is performed within a few minutes. To this extent In time, the temperature will rise only a few centimeters near the surface of the heating coil. Therefore, a lot of heating coils are necessary, and the space for the adsorption tower becomes large. The temperature unevenness is generated in the adsorbent layer, and the loss of heating steam is increased. The disclosure of the invention reveals that the purpose of the present invention is to provide ... The size of the paper containing hydrocarbon vapor agent -5- This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm), and it is consumed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 565468 A7 B7 V. Description of the invention (3) Gas recovery method and device for hydrocarbon vapor efficiently recovering hydrocarbon vapor. The method for recovering hydrocarbon vapor according to the present invention is characterized in that: the first process of cooling and condensing a gas containing hydrocarbon vapor by a cooling means to remove a part of the above-mentioned hydrocarbon vapor, and by heating Means to heat the gas from which a portion of the hydrocarbon vapor has been removed, to raise the temperature of the second process, and to provide the above-mentioned temperature-increased gas to an adsorption means that is filled with an adsorbent. Here, the adsorption is removed The third process of the aforementioned hydrocarbon vapor. The temperature of the gas after the first process treatment exceeds the freezing point of the component and is processed to a low temperature near the freezing point. This temperature increases the lower the temperature, the more the shrinkage increases, and the concentration of the carbon gas vapor in the gas decreases. Therefore, the load in the latter stage becomes smaller, and the adsorption tower of the adsorption means can be made smaller. For example, in the case where benzene becomes the main component of the hydrocarbon vapor, the freezing point is 5 · 5 C, preferably 6 to 20 ° C, and more preferably 6 to 10 ° C. By such a first process, for example, toluene, xylene, xylene, coumarone, indene, etc. are contained in crude light oil containing benzene as a main component, which is produced by carbonization of carbon. Impurities with high boiling points, especially naphthalene, which is a sublimable solid, can be effectively removed by lowering the cooling vapor pressure and dissolving p-benzene. The temperature of the gas heated in the second process is preferably heated to a temperature that is 5 to 30 ° C higher than the temperature of the first process. It is more preferably a temperature of 10 to 20 ° C. This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -6-Please read the note on the back page 565468 A7 B7 V. Invention. Note (4) The reason for setting this temperature is: In the treatment of the first process, the reason why the hydrocarbon vapor reaches the saturation state of the temperature at the time of cooling 'is in the middle of the piping or in the absorption tower, and the temperature is further reduced in the winter, such as heat dissipation, which will cause immediate condensation. Or solid precipitated. This phenomenon may cause piping blockage, malfunction of the switching valve, or increase in pressure loss of the suction tower. In contrast, the second process can increase the temperature of the gas after the first process, reduce the saturation of the hydrocarbon vapor, and make it difficult to cause condensation in the piping and the like. In addition, increasing the temperature of the adsorption device at the rear stage can facilitate separation and regeneration after adsorption. Furthermore, by reducing the concentration of the hydrocarbon vapor, and then reducing the load of the third process, the suction tower or the vacuum pump can be miniaturized. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. On the other hand, the adsorbent in the adsorption tower of the third project is adsorbed by the hydrocarbon vapor, the temperature rises, and the separation temperature decreases. When the adsorption amount is several%, the temperature deviation is several ° C. Therefore, if the heating and heating operation of the second process is not carried out, and after the separation operation of the hydrocarbon vapor of the sorbent is completed, the temperature of the sorbent decreases, and if a gas containing a saturated concentration of hydrocarbon vapor is introduced, Causes condensation at the inlet of the adsorption tower and solids precipitate. Conversely, if the temperature of the introduced gas is too high, the adsorption capacity will decrease, and the adsorption efficiency will decrease. As the absorbing agent filled in the absorbing means of the third process, a general absorbing agent such as silica gel, zeolite, alumina gel, activated carbon, etc. can be used. From the viewpoint of safety, it is best to use silica gel, zeolite, alumina gel. It is more desirable to use silica gel that is matured at high temperature or treated with hydrophobic treatment agent. (Mm) 565468 A7 B7 5. Description of the invention (5), or a high silica zeolite with a silicon / alumina ratio of 80 or more. The sorbent, such as absorbing water in the gas, is necessary to separate the water from the recovered oil. Although it is not easy to absorb water, it is preferred to adsorb so-called hydrophobic sorbents that adsorb hydrocarbons. The so-called adsorption means is, for example, an adsorption tower. In this third process, the hydrocarbon vapor is adsorbed and removed by the adsorbent, and the cleaned gas is discharged. Further, in the third process, the adsorbent adsorbing hydrocarbons is decompressed, and the hydrocarbons are separated and regenerated. The degree of vacuum at the time of separation is preferably below 60 τ r r. More preferably, it is equal to or less than 25 Torr. The lower the absolute pressure, the easier it is for hydrocarbon vapors to separate. The sorbent such as hydrocarbons is not sufficiently separated. At the next adsorption operation, the hydrocarbon vapors are not easily adsorbed, and the removal efficiency of the hydrocarbon vapors is reduced. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs On the other hand, the hydrocarbon vapor separated by the sorbent becomes a very high concentration, which is easily condensed into a liquid and recovered by cooling. The cooling method can generally use a heat exchanger (tube, plate, etc.). In addition, the low-concentration hydrocarbon vapor that cannot be condensed can be processed outside the device without being excluded from the device by mixing the raw material gas at the inlet of the device. Other recovery methods of hydrocarbon vapors can also be contacted with cooling light oil, kerosene, gasoline, recycled oil, etc., to cool and condense them, or dissolve them to recover them. In addition, low-concentration hydrocarbon vapors that cannot be condensed or dissolved can be mixed with the raw material gas at the inlet of the device in the same way as above. -8- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 565468 A7 B7 V. Description of the invention (6) Furthermore, the separated hydrocarbon vapor may be mixed with the gas containing the hydrocarbon vapor of the first process, and then cooled and condensed for recovery. In addition, the target gas for recovering the hydrocarbon vapor is usually air, and a gas similar to nitrogen or other inert gas may be used. It can be suitably applied to the production or storage equipment of liquefied hydrocarbon from the source of the hydrocarbon vapor. Wait for various gases to be discharged. In the recovery method of the present invention, it is desirable that in the first process, the condensed liquid hydrocarbon is used, and the cooled liquid hydrocarbon is brought into contact with a gas containing a hydrocarbon vapor to cool the condensed gas. Hydrocarbon vapor. For this reason, the above-mentioned condensed liquid hydrocarbon can be efficiently recovered.

於本發明之回收方法中，期望在第2工程，使用溫水 做爲加熱上述碳氫化合物蒸氣之一部份被去除之氣體之熱 媒體。 V 經濟部智慧財產局員工消費合作社印製 即，如使用蒸氣做爲熱媒體，與製程氣體之溫度差大 之故，在製程氣體流量變化之情形，會有引起加熱不良或 異常升溫之可能性’並不適合。另一方面，在使用溫水做 爲熱媒體之情形，沒有此種問題。又，透過熱交換器，使 用以蒸氣把水加熱之溫水則無問題。 於本發明之回收方法中，期望在第3工程，將由第2 工程被升溫之氣體供給於吸著手段，使碳氫化合物蒸氣吸 著在吸著劑後，減壓上述吸著手段，在此吸著手段內逆流 -9 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 565468 A7 ____ B7 五、發明說明（7 ) 淸淨氣體（通常之空氣或適當之氣體），在此狀態，使碳 氫化合物由吸著劑分離。 如此，將碳氫化合物由吸著劑分離之際，藉由由吸著 塔之出口側往內部逆流淸淨氣體，碳氫化合物蒸氣之分壓 下降之故，碳氫化合物類容易由吸著劑分離。 此際，淸淨氣體之流量愈多，碳氫化合物類之分離雖 然愈谷易’但是，如單純增加，分離氣體中之碳氣化合物 蒸氣之濃度減少，藉由後工程之冷卻凝縮之回收變得困難 。因此，淸淨氣體之流量存在最適當値，對於被導入吸著 時之吸著塔之製程氣體之流量，最好爲其之1 / 5〜 1/5〇，更好爲1/1〇〜1/2〇。 本發明之回收方法期望設置複數的吸著手段，將這些 吸著手段交互切換爲吸著處理與分離處理以連續處理之。 上述吸著手段之切換以1小時內爲佳，更好爲1 0分 鐘以內。在藉由使碳氫化合物之吸著量之變化小，以使得 吸著劑層之溫度變化小，以短時間之切換較爲理想。 一般，吸著熱係屬發熱，一方面溫度如上升，不容易 吸著（變成容易分離），反之，溫度如下降，容易吸著（ 變成不易分離）。因此，如吸著碳氫化合物蒸氣，吸著劑 之溫度上升，那以上之碳氫化合物蒸氣之吸著變得困難。 反之，於分離操作上，如分離碳氫化合物蒸氣，溫度下降 ，那以上之碳氫化合物蒸氣之分離變得困難。即如進行吸 著·分離操作，產生抵消該操作之效果之方向的現象。因 此，爲了使此種影響變小，提早吸著處理與分離處理之切 (請先閱讀背面之注意事項再填寫本頁)In the recovery method of the present invention, in the second process, it is desirable to use warm water as a heat medium for heating the gas from which a part of the hydrocarbon vapor is removed. V Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, ie, if steam is used as the heat medium, the temperature difference between the process gas and the process gas may cause poor heating or abnormal temperature rise when the process gas flow rate changes. 'Not suitable. On the other hand, in the case of using warm water as a heat medium, there is no such problem. There is no problem with warm water that is heated by steam through a heat exchanger. In the recovery method of the present invention, it is desirable that in the third process, the gas heated by the second process is supplied to the adsorption means so that the hydrocarbon vapor is adsorbed on the adsorbent, and the adsorption means is decompressed. Countercurrent within suction means -9-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 565468 A7 ____ B7 V. Description of Invention (7) Gas (usually air or a suitable gas) in which hydrocarbons are separated from the sorbent. In this way, when separating hydrocarbons from the sorbent, by purging the gas countercurrently from the outlet side of the sorption tower to the inside, the partial pressure of the hydrocarbon vapor is reduced, and the hydrocarbons are easily separated from the sorbent. Separation. At this time, the more the flow rate of the tritium net gas, the easier the separation of hydrocarbons is, but if it is simply increased, the concentration of the carbon gas vapor in the separated gas decreases, which is changed by the post-engineering cooling condensation recovery. Got difficult. Therefore, the flow rate of the net gas is the most appropriate. For the flow rate of the process gas to be introduced into the adsorption tower, the flow rate is preferably 1/5 to 1 / 5〇, more preferably 1 / 1〇 ~ 1/20. In the recovery method of the present invention, it is desirable to provide a plurality of adsorption means, and alternately switch these adsorption means to adsorption processing and separation processing for continuous processing. The switching of the adsorption means is preferably performed within 1 hour, and more preferably within 10 minutes. Since the change in the amount of adsorbed hydrocarbons is small so that the temperature change in the sorbent layer is small, it is preferable to switch in a short time. Generally, the heat of adsorption is heat generation. On the one hand, if the temperature rises, it is not easy to adsorb (becomes easy to separate). On the other hand, if the temperature is lowered, it is easy to adsorb (becomes difficult to separate). Therefore, if the hydrocarbon vapor is adsorbed, the temperature of the adsorbent rises, so that the adsorption of the hydrocarbon vapor above becomes difficult. On the other hand, in the separation operation, if the hydrocarbon vapor is separated and the temperature decreases, the separation of the hydrocarbon vapor above becomes difficult. That is, if the adsorption and separation operation is performed, a phenomenon that cancels the effect of the operation occurs. Therefore, in order to reduce this effect, the suction and separation treatment should be performed early (please read the precautions on the back before filling this page)

訂---------線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -10- 565468 A7 B7 五、發明說明（8 ) 換時間最爲有效。 於本發明之回收方法中，期望將由吸著劑分離之碳氫 化合物與含有第1工程之碳氫化合物蒸氣之氣體混合，冷 卻凝縮加以回收。 分離之碳氫化合物爲非常高之濃度，容易凝縮之故， 藉由將其混合於第1工程之氣體處理之，可以簡單凝縮容 易回收。此方法以冷卻凝縮·回收裝置1個即可，也富經 濟性。 本發明之碳氫化合物蒸氣之回收裝置之特徵爲具備： 冷卻凝縮含有碳氫化合物蒸氣之氣體，去除上述碳氫化合 物蒸氣之一部份之冷卻手段，以及加熱上述碳氫化合物蒸 氣之一部份被去除之氣體，以使之升溫用之加熱手段，以 及被塡充吸著去除上述被升溫之氣體中之碳氫化合物蒸氣 之吸著劑之吸著手段。 上述冷卻手段因應碳氫化合物蒸氣之濃度或被容許之 g力損失，由下述二者被適當選擇之。 容許壓力損失高之情形，適合組合通常之熱交換器（ 管式、板式等）與氣液分離器者。 容許壓力損失低之情形，適合內藏熱交換器之回收塔 ，或外加熱交換器之回收塔。 此回收塔係在上部設置氣液接觸部，在下部設置液體 儲存部者，以泵抽出下部之液體，將其導入上部以循環之 〇 氣液接觸部係被塡充腊希格環（Raschig ring)等之塡 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再_寫本頁) 訂---------線 經濟部智慧財產局員工消費合作社印製 -11 - 565468 A7 B7 五、發明說明（9 ) 充物者，可以有效率地進行氣液之接觸。 (請先閱讀背面之注意事項再填寫本頁) 液體儲存部之液體高度藉由利用泵之打出量與循環量 之平衡而被控制。 在回收塔之氣體之出口部份最好設置除霧器以防止飛 沬。 上述加熱手段可以使用管式、板式等之通常的熱交換 器。 於本發明之回收裝置中，做爲供給於上述冷卻手段之 冷卻用熱媒體之供給源以及供給於上述加熱手段之加熱用 熱媒體之供給源，期望設置共通之交換單元。 如使用共通之交換單元，以1台可以分別供應冷卻用 熱媒體以及加熱用熱媒體之故，具有經濟性，空間上也相 當有利。 又，上述冷卻手段以及加熱手段也可以利用冷凍機或 加熱器。 本發明之回收裝置期望上述吸著手段爲了吸著處理與 分離處理交互切換連續處理，能夠設置複數個。 經濟部智慧財產局員工消費合作社印製 吸著手段之例如吸著塔雖可以爲1塔，但是期望設置 複數之吸著塔，一邊切換吸著·分離操作，一邊連續地進 行吸著處理。 實施發明用之最好形態 【第1實施形態】 參照圖1說明本發明之第1實施形態之碳氫化合物蒸 -12- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 565468 A7 B7 五、發明，說明（1〇 ) 氣之回收方法及其裝置。 本貫施形態之碳氫化合物蒸氣之回收裝置係由具備： 被連接於包含碳氫化合物蒸氣之氣體（此處爲空氣）之導 入管1 0之第1熱交換器1 1，及透過氣體供給管1 0A 被連接於此熱交換器1 1之氣液分離器1 3，及透過氣體 供給管1 2被連接於此氣液分離器1 3之第2熱交換器 1 4，及透過下流側分歧之氣體供給管1 2 A被連接於此 第2熱交換器1 4之第1及第2吸著塔1 5、1 6，及透 過由這些氣體供給管1 2A之吸著塔1 5、1 6附近部份 分歧之氣體供給管3 3 A被連接之真空泵2 0而構成。 在上述第1熱交換器（管式或板式）1 1附設冷凍機 17。 上述氣液分離器1 3被連接於包含碳氫化合物蒸氣之 氣體（此處爲空氣）之導入管1 0之第1熱交換器1 1， 及透過氣體供給管10A被連接於此熱交換器11之氣液 #離器1 3，及透過氣體供給管1 2被連接於此氣液分離 器1 3之第2熱交換器1 4，及透過下流側分歧之氣體供 給管12A被連接於此第2熱交換器14之第1及第2吸 著塔1 5、1 6，及透過由這些氣體供給管1 2A之吸著 塔1 5、1 6附近部份分歧之氣體供給管3 3 A被連接之 真空泵2 0而構成。 在上述第2熱交換器（管式或板式）1 4附設加熱機 2 1。此熱交換器1 4之加熱媒體爲溫水。 上述第1及第2吸著塔1 5、1 6在其內部具有被塡 --------訂---------線I (請先閱讀背面之注意事項再_寫本頁) 拜填寫太 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- 565468 A7 B7 五、發明說明（11) 充吸著劑之吸著層2 2。 在由上述第2熱交換器14往第1及第2吸著塔15 、16之各氣體供給管12設置第1及第2閥23、24 〇 在由上述氣體供給管1 2 A分歧之氣體供給管3 3 a 設置第3及第4閥25、26。 上述第1及第2吸著塔1 5、1 6在其塔頂部分別被 連接淸淨氣體之排出管31，在各管31設置第5及第6 閥 2 7、2 8。 又，在第5及第6閥27、28與吸著塔15、16 之塔頂部之間之管3 1連接使淸淨氣體（此處爲淸淨空氣 )逆流於各吸著塔1 5、1 6之淸淨空氣之供給管3 2 ’ 在各管設置第7及第8閥29、30。 在上述真空泵2 0與上述第1熱交換器1 1前之導入 管1 0之間設置使分離之碳氫化合物蒸氣返回之返回管 3 3 〇 使用此回收裝置以回收碳氫化合物蒸氣之順序，如下 經濟部智慧財產局員工消費合作社印製 首先，第1工程：將包含碳氫化合物蒸氣之空氣由導 入管1 0通過第1熱交換器1 1，在此冷卻此空氣，凝縮 碳氫化合物蒸氣，將此冷卻凝縮之碳氫化合物與空氣供給 於氣液分離器1 3，進行氣液分離。凝縮之一部份之碳氫 化合物蒸氣被儲存於液體儲存部1 9而被回收。另一方面 ，包含剩餘之碳氫化合物蒸氣之空氣由出口被供給於第2 -14- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565468 經濟部智慧財產局員工消費合作社印製 A7 B7 _ 五、發明說明（12 ) 熱交換器1 4。 接著，第2工程：於第2熱交換器1 4中，使用溫水 做爲熱媒體，加熱碳氫化合物蒸氣之一部份被去除之空氣 ，以使之升溫。 接著，第3工程：將上述升溫之空氣供給於第1或第 2吸著塔1 5、1 6，於此，藉由吸著劑吸著去除上述碳 氫化合物蒸氣。 這些第1與第2吸著塔15、16切換閥23、24 、27、28，交互切換吸著處理與分離處理，連續處理 碳氫化合物蒸氣。 在分離處理之際，藉由真空泵2 0以使吸著塔1 5、 1 6減壓，在此吸著塔1 5、1 6內藉由淸淨空氣供給管 3 2使淸淨空氣逆流，在此狀態將碳氫化合物由吸著劑分 離之。 分離之碳氫化合物被送回熱交換器1 1之入口側，與 含有碳氫化合物蒸氣之空氣混合，重複上述第1工程以後 之動作，加以冷卻凝縮回收之。 【第2實施形態】 參考圖2說明本發明之第2實施形態之碳氫化合物蒸 氣之回收方法及裝置。 本實施形態之碳氫化合物蒸氣之回收裝置係由具備： 被連接於包含碳氫化合物蒸氣之氣體（此處爲空氣）之導 入管1 0之回收塔3 6，及在此回收塔3 6之下部與上部 G氏張尺度適用中關家標準（CNS)A4規格（210 X 297公爱)口 5 - (請先閱讀背面之注意事項再_寫本頁) 訂---------線k 565468 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（13 ) 之間透過液狀之碳氫化合物之循環管3 9被設置之第1熱 父換益1 1 1 ’及透過氣體供給管1 2被連接於此回收塔 3 6之第2熱交換器1 4 ’及透過下流側分歧之氣體供給 管12A被連接於此第2熱交換器14之第1及第2吸著 塔1 5、1 6，及透過由這些氣體供給管丄2 A之吸著塔 1 5、1 6附近部份分歧之氣體供給管3 3 A被連接之真 空泵2 0而構成。 上述回收塔3 6在上部設置氣液接觸部3 7，在下部 設置液體儲存部3 8。氣液接觸部3 7係被塡充腊希格環 者。在回收塔3 6之氣體出口部設置網線式除霧器（未圖 示出）。 上述液狀碳氫化合物之循環管3 9其之一方被連接於 回收塔3 6之液體儲存部3 8側，其之另一方被***回收 塔3 6內之氣液接觸部3 7之上方，端部具備液狀碳氫化 合物之散佈器4 1。在此循環管3 9之液體儲存部3 8與 第1熱交換器1 1之間設置循環泵4 2。 此裝置之其它構成部份，例如第1熱交換器1 1、第 2熱交換器14、第1及第2吸著塔15、16、真空泵 2 0等，與上述第1實施形態相同。 利用此回收裝置以回收碳氫化合物蒸氣之順序，如下 述者： 首先，第1工程··將含碳氫化合物蒸氣之空氣由導入 管1 0供給於回收塔3 6，於此，冷卻空氣’凝縮碳氫化 合物蒸氣，將產生液體儲存於液體儲存部3 8。冷卻凝縮 請 先 閱 讀 背 面 之 注 意 事 項 再/ 填< 寫 本 頁Order --------- line · This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -10- 565468 A7 B7 V. Description of the invention (8) Change time is most effective. In the recovery method of the present invention, it is desirable that the hydrocarbon separated by the sorbent is mixed with the gas containing the hydrocarbon vapor of the first process, and cooled and condensed to recover. The separated hydrocarbon has a very high concentration and is easy to condense. By mixing it with the gas treatment of the first process, it can be easily condensed and easily recovered. This method requires only one cooling condensation / recovery device and is also economical. The hydrocarbon vapor recovery device of the present invention is characterized by having: a cooling means for cooling and condensing a gas containing a hydrocarbon vapor, removing a part of the hydrocarbon vapor, and heating a part of the hydrocarbon vapor Heating means for heating the gas to be removed, and absorbing means for adsorbing the adsorbent for removing the hydrocarbon vapor in the heated gas by suction. The above cooling means is appropriately selected from the following two depending on the concentration of the hydrocarbon vapor or the allowable g-force loss. In the case of high allowable pressure loss, it is suitable for the combination of ordinary heat exchangers (tube, plate, etc.) and gas-liquid separators. In the case of low allowable pressure loss, it is suitable for a recovery tower with a built-in heat exchanger or a recovery tower with an external heat exchanger. This recovery tower is provided with a gas-liquid contact part in the upper part and a liquid storage part in the lower part. The liquid in the lower part is pumped out and introduced into the upper part for circulation. The gas-liquid contact part is filled with a Raschig ring. ), Etc. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page) Order --------- Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives -11-565468 A7 B7 V. Description of the invention (9) Fillers can efficiently contact gas and liquid. (Please read the precautions on the back before filling this page.) The liquid height in the liquid storage section is controlled by using the balance between the output and circulation of the pump. It is best to set a mist eliminator in the gas outlet of the recovery tower to prevent flying. As the heating means, a general heat exchanger such as a tube type or a plate type can be used. In the recovery device of the present invention, it is desirable to provide a common exchange unit as a supply source of the cooling heat medium supplied to the cooling means and a supply source of the heating heat medium supplied to the heating means. If a common exchange unit is used, one unit can supply the cooling heat medium and the heating heat medium separately, which is economical and space-efficient. The cooling means and heating means may be a refrigerator or a heater. The recovery device of the present invention expects that the adsorption means described above can be provided with a plurality of adsorption means in order to switch the continuous process between the adsorption process and the separation process. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, although the adsorption tower can be one tower, it is desirable to install a plurality of adsorption towers, and continuously perform adsorption processing while switching the adsorption and separation operations. Best Mode for Carrying Out the Invention [First Embodiment] Referring to FIG. 1, the hydrocarbon steaming of the first embodiment of the present invention will be described. 12- This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm). ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 565468 A7 B7 V. Invention, description (10) Gas recovery method and device. The hydrocarbon vapor recovery device in this embodiment is provided with: a first heat exchanger 11 connected to an introduction pipe 10 of a gas (here, air) containing a hydrocarbon vapor, and a permeate gas supply The pipe 10A is connected to the gas-liquid separator 13 of the heat exchanger 11 and the permeate gas supply pipe 12 is connected to the second heat exchanger 14 of the gas-liquid separator 13 and the permeate downstream side The branched gas supply pipes 1 2 A are connected to the first and second suction towers 15 and 16 of the second heat exchanger 14 and the suction towers 15 and 16 passing through the gas supply pipes 12 and 2A. The gas supply pipe 3 3 A, which is partially divided near 16 is constituted by a vacuum pump 20 connected. A refrigerator 17 is attached to the first heat exchanger (tube or plate type) 1 1. The gas-liquid separator 13 is connected to the first heat exchanger 11 of the introduction pipe 10 of the gas (here, air) containing hydrocarbon vapor, and the permeate gas supply pipe 10A is connected to the heat exchanger. The gas-liquid # 11 separator 11 of 11 and the permeate gas supply pipe 12 are connected to the second heat exchanger 14 of the gas-liquid separator 13 and the gas supply pipe 12A branched through to the downstream side is connected here. The first and second suction towers 15 and 16 of the second heat exchanger 14 and the partially divided gas supply pipes 3 and 3 6 near the suction towers 15 and 16 passing through these gas supply pipes 12A It is constituted by a connected vacuum pump 20. A heater 2 1 is attached to the second heat exchanger (tube or plate type) 1 4. The heating medium of this heat exchanger 14 is warm water. The 1st and 2nd suction towers 1 and 5 above have quilt inside them -------- Order --------- Line I (Please read the precautions on the back before _ (Write this page) Please fill in the paper size of Taiben paper to apply Chinese National Standard (CNS) A4 specification (210 X 297 mm) -13- 565468 A7 B7 V. Description of the invention (11) Sorption layer 2 2 of sorbent. First and second valves 23 and 24 are provided in each of the gas supply pipes 12 from the second heat exchanger 14 to the first and second suction towers 15 and 16. The gas branched by the gas supply pipe 12 A The supply pipe 3 3 a is provided with third and fourth valves 25 and 26. The first and second suction towers 15 and 16 are connected to the exhaust gas pipe 31 of the purge gas at the top of the tower, respectively, and the fifth and sixth valves 27, 28 are provided in each pipe 31. In addition, a pipe 3 1 is connected between the fifth and sixth valves 27 and 28 and the tops of the adsorption towers 15 and 16 so that the purge gas (here, purge air) flows countercurrently to each of the adsorption towers 15 and 5, 1 6 of the clean air supply pipe 3 2 ′ 7th and 8th valves 29 and 30 are provided in each pipe. A return pipe 3 3 is provided between the vacuum pump 20 and the introduction pipe 10 before the first heat exchanger 11 to return the separated hydrocarbon vapor. Using this recovery device to recover the hydrocarbon vapor, Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs First, the first project: Pass the air containing hydrocarbon vapor through the introduction pipe 10 through the first heat exchanger 11 and cool the air here to condense the hydrocarbon vapor The cooled and condensed hydrocarbons and air are supplied to a gas-liquid separator 13 for gas-liquid separation. A part of the condensed hydrocarbon vapor is stored in the liquid storage section 19 and recovered. On the other hand, the air containing the remaining hydrocarbon vapor is supplied from the outlet to Section 2 -14- (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 565468 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _ V. Description of the invention (12) Heat exchanger 1 4. Next, the second process: In the second heat exchanger 14, warm water is used as a heat medium to heat the air from which a portion of the hydrocarbon vapor has been removed to raise the temperature. Next, the third process: the above-mentioned heated air is supplied to the first or second adsorption towers 15 and 16 where the hydrocarbon vapor is removed by adsorption with an adsorbent. These first and second adsorption towers 15 and 16 switch valves 23, 24, 27, and 28, and alternately switch the adsorption processing and separation processing to continuously process hydrocarbon vapors. During the separation process, the suction towers 15 and 16 are depressurized by the vacuum pump 20, and the clean air supply pipe 32 is used to reverse the clean air in the suction towers 15 and 16. In this state, hydrocarbons are separated from the sorbent. The separated hydrocarbons are returned to the inlet side of the heat exchanger 11 and mixed with air containing hydrocarbon vapors, and the operations after the above-mentioned first process are repeated, and they are cooled, condensed, and recovered. [Second Embodiment] A method and an apparatus for recovering hydrocarbon vapor according to a second embodiment of the present invention will be described with reference to FIG. The hydrocarbon vapor recovery device of this embodiment is provided with: a recovery tower 3 6 connected to an introduction pipe 10 of a gas (here, air) containing a hydrocarbon vapor, and a recovery tower 36 The lower and upper G-scale scales are applicable to the Zhongguanjia Standard (CNS) A4 specification (210 X 297 public love) port 5-(Please read the precautions on the back before writing this page) Order -------- -Line k 565468 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (13) Circulation tube of liquid hydrocarbons passing through the liquid 3 9 The first hot parent exchange benefit 1 1 1 ' The second heat exchanger 1 4 ′ connected to the recovery tower 36 and the permeate gas supply pipe 12 are connected to the first and second gas exchangers 14A of the second heat exchanger 14. The suction towers 15 and 16 and a vacuum pump 20 connected to the gas supply pipes 3 3 A which are partially divided near the suction towers 15 and 16 by the gas supply pipes A 2 A are configured. The recovery tower 36 is provided with a gas-liquid contact portion 37 in an upper portion and a liquid storage portion 38 in a lower portion. The gas-liquid contact part 37 is a person who has been filled with a Rasig ring. A network-type demister (not shown) is installed at the gas outlet of the recovery tower 36. One of the above-mentioned liquid hydrocarbon circulation pipes 39 is connected to the liquid storage portion 38 side of the recovery tower 36, and the other is inserted above the gas-liquid contact portion 37 in the recovery tower 36, The end is provided with a liquid hydrocarbon spreader 41. A circulation pump 4 2 is provided between the liquid storage portion 38 of the circulation pipe 39 and the first heat exchanger 11. Other components of the device, such as the first heat exchanger 11, the second heat exchanger 14, the first and second suction towers 15 and 16, and the vacuum pump 20 are the same as those in the first embodiment. The procedure for recovering hydrocarbon vapors using this recovery device is as follows: First, the first process ... The air containing hydrocarbon vapors is supplied to the recovery tower 36 from the introduction pipe 10, and here, the cooling air is cooled. The hydrocarbon vapor is condensed, and the generated liquid is stored in the liquid storage portion 38. Cooling and Condensation Please read the notes on the back and fill in < write this page

訂 線 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -16- 565468 A7 B7 五、發明說明（14) 上述空氣之際，將液體儲存部3 8之液狀碳氫化合物透過 循環管3 9，使其一部份循環，將此於第1熱交換器1 1 冷卻後，供給於回收塔3 6，在氣液接觸部3 7使此液狀 碳氫化合物與上述空氣進行接觸。 此後之第2工程以及第3工程與上述第1實施形態相 同。 又，在第1及第2實施形態中，雖在第1熱交換器 1 1設置冷凍機1 7，在第2熱交換器1 4附設加熱機 2 1，也可以設置共通之交換單元以做爲供給於第1熱交 換器1 1之冷卻用熱媒體之供給源及供給於第2熱交換器 1 4之加熱用熱媒體之供給源。 又，回收塔3 6也可以如下述般地構成之。 經濟部智慧財產局員工消費合作社印製 如圖4所示般地，在回收塔3 6之氣液接觸部3 7與 循環管3 9之導入部之間設置煙囪式托盤或多孔托盤等之 氣液分散器3 7A，在比循環管3 9之導入部還上方之部 份設置除霧器3 7 B。又，在液體儲存部3 8連接由回收 塔3 6之側面至循環泵4 2之取出管4 2 A，其之吸入端 部向下之同時，在其周圍裝置由被配置爲放射狀之複數的 板材形成之渦流制止器4 2 B。 由於設置氣液分散器3 7 A，可以謀取由循環管3 9 返回之液相成分與通過氣液接觸部3 7上升而至之氣相成 分之更多接觸，可以促進液相成分之回收。又，由於設置 除霧器3 7 B，可以由被取出於塔頂之氣體供給管1 2之 氣體去除霧狀之液相成分。再者，藉由設置渦流制止器 -17- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565468 A7 B7 五、發明說明（15) 4 2 B ’可以避免由取出管4 2 A吸取儲存於液體儲存部 3 8之液體成分之際之渦流以及氣體捲入之產生。 這些之氣液分散器3 7 A、除霧器3 7 B、渦流制止 器4 2 B之具體構造，可以適當採用以既存之工廠技術被 利用之構造。 如圖5所示般地，可以採用略u字型之回收塔3 6A 。圖中’在略U字型之回收塔3 6 A之其中一方之塔頂（ 圖中左側）連接導入管1 〇，在該塔頂之稍微下方處連接 循環管3 9。在循環管3 9之接觸部份稍微下方處設置氣 液分散器3 7 A ’在其下方設置氣液接觸部3 7。在其中 一方之塔頂（圖中右側）連接氣體供給管1 2，在其下方 設置除霧器37B。回收塔36A之下部雖然變寬，但是 與上述圖4之構造相同。 藉由此種略U字型之回收塔3 6 A也可以分離被包含 於由導入管1 0及循環管3 9來之氣體之碳氫化合物蒸氣 ，將碳氫化合物蒸氣被分離之氣體由氣體供給管1 2取出 之同時’可以儲存於液體儲存部3 8。 上述之各實施形態雖係處理由單一之導入管1 〇來之 含有碳氫化合物蒸氣之氣體者，但是，也可以當成處理由 複數之氣體原來之含有碳氫化合物蒸氣之氣體者。在此種 情形，期望在各氣體源之間補上可以避免由於逆流等所導 致之混合污染之構造。 圖6中，在回收塔3 6A連接2系統之導入管1〇l ，1 0H。導入管1 〇 L與圖5之導入管1 〇相同地被連 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)The paper size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -16- 565468 A7 B7 V. Description of the invention (14) In the case of the above air, the liquid hydrocarbons in the liquid storage section 3 8 The compound passes through the circulation pipe 39 to circulate a part of it. After cooling this in the first heat exchanger 1 1, it is supplied to the recovery tower 36. The gas-liquid contact portion 37 makes the liquid hydrocarbon and the above-mentioned liquid hydrocarbon Contact with air. The second and third processes thereafter are the same as the first embodiment. In addition, in the first and second embodiments, although a refrigerator 17 is provided in the first heat exchanger 11 and a heater 21 is attached to the second heat exchanger 14, a common exchange unit may be provided. It is the supply source of the cooling heat medium supplied to the first heat exchanger 11 and the supply source of the heating heat medium supplied to the second heat exchanger 14. The recovery tower 36 may be configured as described below. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, as shown in FIG. 4, a gas such as a chimney tray or a perforated tray is installed between the gas-liquid contact portion 37 of the recovery tower 36 and the introduction portion of the circulation pipe 39. The liquid disperser 3 7A is provided with a demister 37 B at a portion above the introduction portion of the circulation pipe 39. In addition, the liquid storage portion 38 is connected to the extraction pipe 4 2 A from the side of the recovery tower 36 to the circulation pump 4 2, and the suction end of the liquid storage portion 38 is directed downward. The eddy current stop 4 2 B formed by the sheet. Since the gas-liquid disperser 3 7 A is provided, more liquid-phase components returned from the circulation pipe 3 9 can be brought into contact with more gas-phase components ascended through the gas-liquid contact portion 37 to promote recovery of the liquid-phase components. Furthermore, since the mist eliminator 3 7 B is provided, the gas-like liquid component can be removed by the gas taken out from the gas supply pipe 12 at the top of the tower. Furthermore, by setting the eddy current stopper-17- this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 565468 A7 B7 V. Description of the invention (15) 4 2 B 'It is possible to avoid removing the tube 4 2 A generates eddy current and gas entanglement when the liquid components stored in the liquid storage section 38 are sucked. The specific structures of these gas-liquid dispersers 3 7 A, demisters 3 7 B, and vortex arrestors 4 2 B can be appropriately adopted structures that are utilized by existing factory technologies. As shown in Fig. 5, a slightly u-shaped recovery tower 36A can be used. In the figure, the introduction pipe 10 is connected to the top of one of the slightly U-shaped recovery towers 3 6 A (the left side in the figure), and the circulation pipe 39 is connected slightly below the top of the tower. A gas-liquid disperser 3 7 A is provided slightly below the contact portion of the circulation pipe 39, and a gas-liquid contact portion 37 is provided below it. A gas supply pipe 12 is connected to the top of one of the towers (the right side in the figure), and a mist eliminator 37B is provided below it. Although the lower part of the recovery tower 36A is widened, the structure is the same as that of Fig. 4 described above. With this slightly U-shaped recovery tower 3 6 A, the hydrocarbon vapor contained in the gas from the introduction pipe 10 and the circulation pipe 39 can be separated, and the gas from which the hydrocarbon vapor is separated can be separated from the gas. At the same time when the supply pipe 12 is taken out, it can be stored in the liquid storage section 38. Each of the embodiments described above deals with a gas containing hydrocarbon vapor from a single introduction tube 10, but it can also be treated as a gas containing hydrocarbon vapor from a plurality of gases. In such a case, it is desirable to add a structure between the gas sources that can avoid mixed pollution due to backflow and the like. In FIG. 6, the introduction pipes 10 and 10H of the 2 system are connected to the recovery tower 36A. The introduction tube 1 〇 is connected in the same way as the introduction tube 1 〇 shown in Figure 5. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)

訂---------線L 經濟部智慧財產局員工消費合作社印製 18 565468 A7 _B7__ 五、發明說明（16 ) 接於塔頂。導入管1 Ο Η被連接於回收塔3 6 A之氣液接 觸部3 7與氣液分散器3 7 A之間。 此處，被供給於導入管1 Ο Η之氣體源比被供給於導 入管1 0 L之氣體源之儲存液體之濃度或純度還高。例如 ，導入管1 0 L被連接於粗苯筒之排氣口，導入管1 0Η 被連接於純苯筒之排氣口。 在此種情形，導入管1 Ο Η如果被單純連接於回收塔 3 6 A，在回收塔3 6 Α內被導入由導入管1 〇 L來之低 純度的苯成分之故，此低純度之苯成分通過導入管1 〇 Η 逆流於純苯筒，成爲使相同筒內苯純度降低之原因。 因此，在導入管1 0Η之導入部份設置密封口 1 〇 Ρ ，在其中儲存透過導入管1 Ο Η被連接之氣體源之內容液 (此處爲純苯）。而且，使導入管1 Q Η之端部浸於密封 口 1 Ο Ρ之內之液相。 藉由此，可以防止由導入管1 Ο Η來之逆流。 又，複數之氣體源並不限於同質者，只要是回收對象 重複，也可以爲汽油與苯等之不同種者。 以下，依據上述之各實施形態進行之具體的實驗例說 明之。 【實驗例1】 於上述第1實施形態中，方法及裝置之具體例設如下 述者。 含有應處理之高濃度碳氫化合物蒸氣之空氣（以下， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -19 - 請 先 閱 讀· 背 面Order --------- Line L Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18 565468 A7 _B7__ V. Description of Invention (16) Connected to the top of the tower. The introduction pipe 10 is connected between the gas-liquid contact portion 37 of the recovery tower 36A and the gas-liquid disperser 37A. Here, the gas source supplied to the introduction tube 10 Η is higher in concentration or purity than the storage liquid supplied to the gas source 10 L of the introduction tube. For example, the introduction tube 10 L is connected to the exhaust port of a crude benzene tube, and the introduction tube 10 L is connected to the exhaust port of a pure benzene tube. In this case, if the introduction pipe 10 Η is simply connected to the recovery tower 3 6 A, a low-purity benzene component from the introduction pipe 10 liter is introduced into the recovery tower 36 6 A. This low-purity The benzene component flows countercurrently through the introduction tube to the pure benzene cylinder, which causes the purity of the benzene in the same cylinder to decrease. Therefore, a sealing port 10p is provided at the introduction part of the introduction pipe 10Η, and the content liquid (here, pure benzene) of the gas source connected through the introduction pipe 10 is stored therein. Then, the end portion of the introduction tube 1 Q Η was immersed in a liquid phase within the seal port 100 P. By this, it is possible to prevent the backflow from the introduction tube 10 Η. Further, the plural gas sources are not limited to those of the same type, and may be different types of gasoline and benzene, as long as the recovery targets are repeated. Hereinafter, specific experimental examples based on the above-mentioned embodiments will be described. [Experimental Example 1] In the first embodiment described above, specific examples of the method and device are as follows. Air containing high-concentration hydrocarbon vapors to be treated (hereinafter, the size of this paper applies to China National Standard (CNS) A4 (210 X 297 mm) -19-Please read · Back

訂 經濟部智慧財產局員工消費合作社印製 565468 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（17 ) 稱爲原料氣體）之流量爲1 0 m 3，碳氫化合物蒸氣之濃度 爲2 0 v ο 1 %。此空氣中之碳氫化合物蒸氣成分如下述 表1 。 (表1 ) 碳氫化合物 種類 正戊烷 苯 甲苯 二甲苯 三甲苯 印 萘 濃度（v〇l%) 2.5 15.0 1.5 0.5 0.2 0.1 0.2 首先，使原料氣體與由真空泵2 0之出口分離之氣體 合流，在管式之第1熱交換器1 1冷卻之，使一部份凝縮 ，導入豎立型之氣液分離器1 3，分離爲氣相與液相。 在第1熱交換器1 1冷卻後之氣體之溫度爲1 0°C。 又，回收之液狀的碳氫化合物量爲3 · 9 k g / h r。 接著，將由氣液分離器1 3出來之氣體導入管式之第 2熱交換器1 4，在此加熱升溫。在此熱交換器1 4被加 熱後之氣體的溫度爲3 0 °C。 接著，將升溫之氣體供給於2塔中之一方之吸著塔 1 5，在此將碳氫化合物蒸氣藉由吸著劑吸著去除之。使 用之吸著劑爲氧化矽膠【富士シ9シ7化學（株）製之氧 化矽膠CARiACT Q — 3 (商品名）】藉由5 0 〇 °C、4小 時之熟成以疏水化處理者。2塔之吸著塔1 5、1 6每5 分鐘切換入口與出口之閥23、24、27、28以交互 進行吸著與分離。Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 565468 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 B7 V. Description of the invention (17) is called raw material gas) The flow rate is 10 m 3 and the concentration of hydrocarbon vapor 2 0 v ο 1%. The hydrocarbon vapor composition in this air is shown in Table 1 below. (Table 1) Hydrocarbon type n-pentane benzene xylene xylene xylene concentration (vOl%) 2.5 15.0 1.5 0.5 0.2 0.1 0.2 First, the raw material gas is merged with the gas separated by the outlet of the vacuum pump 20, The first heat exchanger 11 of the tube type is cooled, and a part of it is condensed, and the gas-liquid separator 13 of an upright type is introduced and separated into a gas phase and a liquid phase. The temperature of the gas after cooling in the first heat exchanger 11 is 10 ° C. The amount of the recovered liquid hydrocarbon was 3.9 k g / h r. Next, the gas from the gas-liquid separator 13 is introduced into the second heat exchanger 14 of the tube type, and the temperature is increased by heating. The temperature of the heated heat exchanger 14 here is 30 ° C. Next, the heated gas is supplied to one of the two absorption towers 15, where the hydrocarbon vapor is removed by adsorption with an adsorbent. The sorbent used was silica gel [Carbon Silicon Oxide CARiACT Q-3 (trade name) manufactured by Fuji XIX 9 Chemical Co., Ltd.], which was hydrophobized by aging at 500 ° C for 4 hours. The adsorption towers 15 and 16 of the two towers switch the inlet and outlet valves 23, 24, 27, and 28 every 5 minutes to interactively perform adsorption and separation.

本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -20- 565468 A7 __B7 _________ 五、發明說明（彳8 ) 吸著塔1 5、1 6出口之氣體中之碳氫化合物蒸氣之* 濃度爲3 0 p pm。又，碳氫化合物蒸氣之成分，係如下* 述表2。 (表2 ) 碳氫化合物 種類 正戊烷 苯 甲苯 二甲苯 三甲苯 -U-U 印 萘 濃度（v〇l%) 0.002 0.001 0 0 0 0 0一 由吸著塔1 5、1 6之吸著劑之碳氫化合物之分離操 作係藉由使吸著塔1 5、1 6內以真空泵2 0減壓以進行 。此時之分離壓爲絕對壓力2 5 Τ ο I·!·。此分離係通過 淸淨空氣之供給管3 2，由吸著塔1 5、1 6之出口對內 部以1 m 3 / h r之流量一邊逆流淸淨空氣一邊進行之。 由真空泵2 0之出口之分離氣體使之與導入管1 0之 原料氣體合流，以第1熱交換器1 1冷卻凝縮回收之。 以***吸著塔1 5、1 6之熱電對量測吸著·分離時 之吸著劑之溫度時，在吸著時，最高爲3 5 °C，分離時， 最低爲2 5 °C。 運轉中，吸著塔1 5、1 6之壓力損失爲20 m m Η 2〇，幾乎爲一定，運轉終了後，進行吸著塔1 5、 1 6與配管之開放檢查，並沒有發現碳氫化合物蒸氣之凝 縮等之異常。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -20- 565468 A7 __B7 _________ V. Description of the invention (彳 8) Suction of the hydrocarbons in the gas at the outlet of the towers 1, 5 and 16 The concentration of vapour * is 30 p pm. The components of the hydrocarbon vapor are shown in Table 2 below. (Table 2) Hydrocarbon type n-pentane benzene xylene xylene xylene-UU naphthalene concentration (vOl%) 0.002 0.001 0 0 0 0 0 0 The hydrocarbon separation operation is performed by depressurizing the suction towers 15 and 16 with a vacuum pump 20. The separation pressure at this time is an absolute pressure of 2 5 Τ I ·! ·. This separation is carried out through the supply pipe 32 of clean air, and from the outlets of the suction towers 15 and 16 to the inside at a flow rate of 1 m 3 / h r while the clean air is countercurrently flowed. The separated gas from the outlet of the vacuum pump 20 is merged with the raw material gas of the introduction pipe 10, and cooled and condensed by the first heat exchanger 11 to recover it. When measuring the temperature of the sorbent during adsorption and separation using thermoelectric pairs inserted in the adsorption towers 15 and 16, the maximum temperature during adsorption is 3 5 ° C, and the minimum temperature during separation is 2 5 ° C. During the operation, the pressure loss of the adsorption towers 15 and 16 was 20 mm Η 20, which was almost constant. After the end of the operation, the opening inspection of the adsorption towers 15 and 16 and the piping was performed. No hydrocarbons were found. Vapor condensation and other abnormalities. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-21 - 565468 A7 B7 五、發明說明（19) 【實驗例2】 請 先 閱 讀 背 面 之 注 意 事 項 再 填 寫 本 頁 於上述第2實施形態中，方法及裝置之具體例設如T 述者。 含有應處理之高濃度碳氫化合物蒸氣之空氣係與# _ 例1相同者。 首先，使原料氣體與由真空泵2 0之出口分離之氣11 合流，導入豎立型之回收塔3 6。將此回收塔3 6之液體 儲存部1 9之液體以泵4 2抽出，以管式之第1熱交換器 1 1冷卻後，導入回收塔3 6之上部，使與原料氣體接觸 ，凝縮原料氣體中之碳氫化合物蒸氣。以熱交換器1 1冷 卻後之氣體之溫度爲1 0 °C。 在此分離氣液接觸後之氣相與液相，氣相由回收塔 3 6之上部抽出，液相回收於下部之液體儲存部3 8。回 收之液狀的碳氫化合物量爲3 · 9 k g / h I·。 接著，將由回收塔3 6出來之氣體導入板式之第2熱 交換器1 4，於此加溫之。以此熱交換器1 4加熱後之氣 體之溫度爲2 5 °C。 經濟部智慧財產局員工消費合作社印製 接著，將升溫之氣體供給於2塔中之其中一方之吸著 塔1 5，在此藉由吸著劑吸著去除碳氫化合物蒸氣。使用 之吸著劑爲氧化矽膠【富士シ卩シ7化學（株）製之氧化 矽膠CARiACT Q — 6 (商品名）】藉由5〇〇°C、4小時 之熟成以疏水化處理者。2塔之吸著塔1 5、1 6每5分 鐘切換入口與出口之閥23、24、27、28以交互進 行吸著與分離。 -22- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 565468 A7 __ B7 五、發明說明（2〇 ) 吸著塔1 5、1 6出口之氣體中之碳氬化合物蒸氣之 濃度爲3 0 p p m。又，碳氫化合物蒸氣之成分，係如下 述表3。 (表3 ) 碳氫化合物 種類 正戊烷 苯 甲苯 二甲苯 三甲苯 茚 萘 濃度（v ο 1 %) 0.002 0.001 0 0 0 0 0 由吸著塔1 5、1 6之吸著劑之碳氫化合物之分離操 作係藉由使吸著塔1 5、1 6內以真空泵2 0減壓以進行 。此時之分離壓爲絕對壓力2 Ο T 〇 r r。此分離係通過 淸淨空氣之供給管3 2，由吸著塔1 5、1 6之出口對內 部以0 · 5 m 3 / h r之流量一邊逆流淸淨空氣一邊進行之 〇 由真空泵2 0之出口之分離氣體使之與導入管1 〇之 原料氣體合流，以回收塔3 6冷卻凝縮回收之。 以***吸著塔1 5、1 6之熱電對量測吸著·分離時 之吸著劑之溫度時，在吸著時，最高爲3 0 °C ’分離時’ 最低爲2 0 °C。 運轉中，吸著塔15、16之壓力損失爲20 m m Η 2〇，幾乎爲一定，運轉終了後，進行吸著塔1 5、 1 6與配管之開放檢查，並沒有發現碳氫化合物蒸氣之凝 縮等之異常。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -23 - (請先閱讀背面之注意事項再續寫本頁) 訂---------線k1 經濟部智慧財產局員X消費合作社印製 經濟部智慧財產局員工消費合作社印製 565468 A7 ____ B7 五、發明說明（21) 【比較例1】 如圖3所示般地’本比較例之裝置係由第2實施形態 之裝置去除第2熱交換器1 4，在吸著塔1 5、1 6設置 具有蒸氣流經之加熱盤管4 5之加熱機4 6者。 含有應處理之高濃度碳氫化合物蒸氣之空氣係與實驗 例1相同者。 首先，使原料氣體與由真空泵2 0之出口分離之氣體 合流，導入豎立型之回收塔3 6。將此回收塔3 6之液體 儲存部3 8之液體以泵4 2抽出，以管式之第1熱交換器 1 1冷卻後，導入回收塔3 6之上部，使與原料氣體接觸 ’凝縮原料氣體中之碳氫化合物蒸氣。以熱交換器1 1冷 卻後之氣體之溫度爲1 0 °C。 在此分離氣液接觸後之氣相與液相，氣相由回收塔 3 6之上部抽出，液相回收於下部之液體儲存部3 8。回 收之液狀的碳氫化合物量爲3 . 9 k g / h r。 接著，將由回收塔3 6出來之氣體供給於2塔中之其 中一方之吸著塔1 5，在此藉由吸著劑吸著去除碳氫化合 物蒸氣。使用之吸著劑爲氧化矽膠【富士シUシ7化學（ 株）製之氧化矽膠CARiACT Q — 6 (商品名）】藉由 5〇0 °C、4小時之熟成以疏水化處理者。2塔之吸著塔 1 5、1 6每5分鐘切換入口與出口之閥2 3、24、 2 7、2 8以交互進行吸著與分離。 吸著塔1 5、1 6出口之氣體中之碳氫化合物蒸氣之 濃度爲1 0 0〜2 0 0 P p m，可以見到漸漸增加之傾向 (請先閱讀背面之注意事項再填寫本頁)-21-565468 A7 B7 V. Description of the invention (19) [Experimental Example 2] Please read the notes on the back side and then fill out this page. In the second embodiment above, the specific examples of the method and device are as described in T. The air containing high-concentration hydrocarbon vapors to be treated is the same as # _ Example 1. First, the raw material gas is merged with the gas 11 separated from the outlet of the vacuum pump 20 and introduced into a vertical type recovery tower 36. The liquid in the liquid storage portion 19 of this recovery tower 36 is pumped out by the pump 4 2 and cooled in the first heat exchanger 11 of the tube type, and then introduced into the upper portion of the recovery tower 36 to contact the raw material gas and condense the raw material. Hydrocarbon vapor in the gas. The temperature of the gas cooled by the heat exchanger 11 is 10 ° C. Here, the gas and liquid phases after gas-liquid contact are separated, the gas phase is extracted from the upper part of the recovery tower 36, and the liquid phase is recovered in the lower liquid storage part 38. The amount of recovered liquid hydrocarbon was 3.9 kg / h I ·. Next, the gas from the recovery tower 36 is introduced into the plate-type second heat exchanger 14 and heated there. The temperature of the gas heated by this heat exchanger 14 is 2 5 ° C. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Next, the heated gas is supplied to the adsorption tower 15 of one of the two towers, where the hydrocarbon vapor is removed by adsorption with an adsorbent. The sorbent used was silicon oxide [Carbon Silicone CARiACT Q-6 (trade name) manufactured by Fuji Shiki 7 Chemical Co., Ltd.], which was hydrophobized by aging at 500 ° C for 4 hours. The suction towers 15 and 16 of the two towers switch the inlet and outlet valves 23, 24, 27, and 28 every 5 minutes to interactively perform suction and separation. -22- The size of this paper applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 565468 A7 __ B7 V. Description of the invention (20) Carbon and argon compounds in the gas at the exit of the absorption towers 1 and 16 The concentration of vapor is 30 ppm. The components of the hydrocarbon vapor are shown in Table 3 below. (Table 3) Hydrocarbon type n-pentane benzene xylene xylene indole naphthalene concentration (v ο 1%) 0.002 0.001 0 0 0 0 0 0 The separation operation is performed by decompressing the suction towers 15 and 16 with a vacuum pump 20. The separation pressure at this time is an absolute pressure of 20 〇 〇 r r. This separation is carried out through the supply pipe 3 2 of clean air, and from the outlets of the absorption towers 15 and 16 to the inside at a flow rate of 0.5 m 3 / hr while the clean air is countercurrently flowed. The separated gas at the outlet is merged with the raw material gas of the introduction pipe 10, and is recovered by cooling, condensation, and recovery in the recovery tower 36. When measuring the temperature of the sorbent at the time of adsorption and separation using thermoelectric pairs inserted in the adsorption towers 15 and 16, the highest value during adsorption is 30 ° C and the lowest value is 20 ° C during separation. During operation, the pressure loss of the adsorption towers 15 and 16 was 20 mm Η 20, which was almost constant. After the end of the operation, the open inspection of the adsorption towers 15 and 16 and the piping was performed. No hydrocarbon vapor was found. Abnormalities such as condensation. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -23-(Please read the precautions on the back before continuing on this page) Order --------- line k1 Ministry of Economic Affairs Printed by Intellectual Property Bureau member X Consumer Cooperative Cooperative printed by Ministry of Economic Affairs Intellectual Property Bureau employee Cooperative Cooperative printed 565468 A7 ____ B7 V. Description of Invention (21) [Comparative Example 1] As shown in FIG. The apparatus according to the second embodiment removes the second heat exchanger 14 and installs a heating machine 4 6 having heating coils 4 5 through which steam flows through the suction towers 15 and 16. The air containing the high-concentration hydrocarbon vapor to be treated is the same as in Experimental Example 1. First, the raw material gas is merged with the gas separated from the outlet of the vacuum pump 20 and introduced into a vertical type recovery tower 36. The liquid in the liquid storage portion 38 of this recovery tower 36 is pumped out by the pump 4 2 and cooled in the first heat exchanger 11 of the tube type, and then introduced into the upper portion of the recovery tower 36 to bring it into contact with the raw material gas. Hydrocarbon vapor in the gas. The temperature of the gas cooled by the heat exchanger 11 is 10 ° C. Here, the gas and liquid phases after gas-liquid contact are separated, the gas phase is extracted from the upper part of the recovery tower 36, and the liquid phase is recovered in the lower liquid storage part 38. The amount of recovered liquid hydrocarbons was 3.9 k g / h r. Next, the gas from the recovery tower 36 is supplied to one of the two towers, the adsorption tower 15, where the hydrocarbon vapor is removed by adsorption with an adsorbent. The sorbent used was silicon oxide [silica oxide CARiACT Q-6 (trade name) manufactured by Fuji Shi Ushi 7 Chemical Co., Ltd.], which was hydrophobized by aging at 5000 ° C for 4 hours. The adsorption towers of 2 towers 1, 5 and 16 switch the inlet and outlet valves 2 3, 24, 2 7, 2 8 every 5 minutes to interactively perform adsorption and separation. The concentration of the hydrocarbon vapor in the gas at the outlet of the suction towers 15 and 16 is 1 0 ~ 2 0 0 P p m, and you can see the tendency of increasing gradually (please read the precautions on the back before filling this page)

訂---------線； 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -24- 565468 Α7 ____Β7___ 五、發明說明（22 ) 。又，第1週間之碳氫化合物蒸氣之成分，係如下述表4 (表4 ) 碳氫化合物 種類 正戊院 苯 甲苯 二甲苯 三甲苯 茚 萘 濃度（v ο 1 %) 0.12 0.06 0.02 0 0 0 0 由吸著塔1 5、1 6之吸著劑之碳氫化合物之分離操 作係藉由使吸著塔1 5、1 6內以真空泵2 0減壓以進行 。此時之分離壓爲絕對壓力2 Ο T 〇 r r。此分離係由吸 者ί合1 5、1 6之出口以0 · 5m /h r之流量一邊逆流 淸淨空氣一邊進行之。 由真空泵2 0之出口之分離氣體使之與裝置入口之原 料氣體合流，以回收塔3 6冷卻凝縮回收之。 以熱電對量測吸著·分離時之吸著劑之溫度時，在吸 著時，最高爲1 5°C，分離時，最低爲1 0°C、最高爲 4〇°C，吸著塔1 5、1 6內之偏差很大。 一週間之運轉中，吸著塔1 5、1 6之壓力損失爲 2〇〜3 0 m m Η 2〇，可以見到漸漸增加之傾向。 運轉終了後，進行吸著塔1 5、1 6與配管之開放檢 查，在吸著塔1 5、1 6之下部與配管途中之閥附近可以 見到碳氫化合物蒸氣之凝縮。 (請先閱讀背面之注意事項再填寫本頁)Order --------- line; This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) -24-565468 Α7 ____ Β7 ___ V. Description of invention (22). In addition, the components of the hydrocarbon vapor during the first week are as shown in Table 4 below (Table 4). Hydrocarbon type n-pentylbenzene xylene xylene indole naphthalene concentration (v ο 1%) 0.12 0.06 0.02 0 0 0 0 The separation of hydrocarbons from the sorbents in the adsorption towers 15 and 16 is performed by reducing the pressure in the adsorption towers 15 and 16 with a vacuum pump 20. The separation pressure at this time is an absolute pressure of 20 〇 〇 r r. This separation is carried out by the outlets of the suction stations 15 and 16 at a flow rate of 0 · 5m / h r while countercurrently purging the air. The separated gas from the outlet of the vacuum pump 20 is merged with the raw material gas at the inlet of the device, and the recovery tower 36 is cooled and condensed to recover it. When measuring the temperature of the sorbent during adsorption / separation by thermoelectric pairing, the highest temperature is 15 ° C during adsorption, and the lowest is 10 ° C, and the highest is 40 ° C during separation. The deviations within 15 and 16 are large. During one week's operation, the pressure loss of the suction towers 15 and 16 is 20 ~ 30 mm m Η 20, and it can be seen that the tendency gradually increases. After the end of the operation, check the openness of the suction towers 15 and 16 and the piping. Condensation of hydrocarbon vapors can be seen in the lower part of the suction towers 15 and 16 and near the valve in the middle of the piping. (Please read the notes on the back before filling this page)

訂---------养 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 25- 565468 A7 B7 五、發明說明（23 ) 產業上之利用可能性 可以利用於汽油等之液狀碳氫化合物之儲存設備或精 製等之處理設備中，由儲存筒等被排出之碳氫化合物蒸氣 之擴散防止以及回收再利用。 圖面之簡單說明 圖1爲本發明之第1實施形態之碳氫化合物蒸氣之回 收裝置之槪略圖。 圖2爲本發明之第2實施形態之碳氫化合物蒸氣之回 收裝置之槪略圖。 圖3爲比較例之碳氫化合物蒸氣之回收裝置之槪略圖 〇 圖4係顯示本發明之其它實施形態之碳氫化合物蒸氣 之回收裝置之重要部位之槪略圖。 圖5係顯示本發明之其它實施形態之碳氫化合物蒸氣 之回收裝置之重要部位之槪略圖。 一 圖6係顯示本發明之其它實施形態之碳氫化合物蒸氣 之回收裝置之重要部位之槪略圖。 主要元件對照表 I 0 導入管 II 第1熱交換器 1 2 供給管 13 氣液分離器 (請先閱讀背面之注意事項再_寫本頁)Order --------- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economics and Economics. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 25- 565468 A7 B7. 23) Industrial utilization can be used in the storage facilities of liquid hydrocarbons such as gasoline or in processing facilities such as refining, etc., to prevent the diffusion of hydrocarbon vapors discharged from storage tanks and to recycle them. Brief Description of the Drawings Fig. 1 is a schematic view of a hydrocarbon vapor recovery device according to a first embodiment of the present invention. Fig. 2 is a schematic view of a hydrocarbon vapor recovery device according to a second embodiment of the present invention. Fig. 3 is a schematic diagram of a hydrocarbon vapor recovery device of a comparative example. Fig. 4 is a schematic diagram of important parts of a hydrocarbon vapor recovery device according to another embodiment of the present invention. Fig. 5 is a schematic view showing important parts of a hydrocarbon vapor recovery device according to another embodiment of the present invention. Fig. 6 is a schematic diagram showing important parts of a hydrocarbon vapor recovery device according to another embodiment of the present invention. Comparison table of main components I 0 Introduction pipe II First heat exchanger 1 2 Supply pipe 13 Gas-liquid separator (Please read the precautions on the back before writing this page)

訂---------線I 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -26- 565468 A7 B7 五、發明說明（24) 14 第2熱交換器 15， 16 吸著塔 17 冷凍機 2〇 真空泵 2 3, 2 4 ，2 7 ，2 k · ϋ ϋ ϋ ϋ n n J ，a ϋ 1_1 I a^i ·ϋ 1 n I Jw- ▼ 唁 矣l (請先閱讀背面之注意事項再场寫本頁) 1 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -27-Order --------- Line I Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -26- 565468 A7 B7 V. Invention Explanation (24) 14 Second heat exchanger 15, 16 Suction tower 17 Refrigerator 20 Vacuum pump 2 3, 2 4, 2 7, 2 k · ϋ ϋ ϋ ϋ nn J, a ϋ 1_1 I a ^ i · ϋ 1 n I Jw- ▼ 唁 矣 l (Please read the precautions on the back before writing this page) 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed in accordance with China National Standard (CNS) A4 (210 X 297) Mm) -27-

Claims (1)

565468565468 A8B8C8D8 經濟部智慧財產局員工消費合作社印製 、申請專利範圍 1 · 一種碳氫化合物蒸氣之回收方法，其特徵爲具備 :藉由冷卻手段，冷卻凝縮含有碳氫化合物蒸氣之氣體， 以去除上述碳氫化合物蒸氣之一部份之第1工程， 及藉由加熱手段以加熱上述碳氫化合物蒸氣之一部份 被去除之氣體，以提升溫度之第2工程， 以及將上述升溫之氣體供給於被塡充吸著劑之吸著手 段，在此，吸著去除上述碳氫化合物蒸氣之第3工程。 2 ·如申請專利範圍第1項記載之碳氫化合物蒸氣之 回收方法，其中在第1工程使用上述凝縮之液狀碳氫化合 物，使冷卻之此種液狀之碳氫化合物與含有碳氫化合物蒸 氣之氣體接觸，以冷卻凝縮氣體中之碳氫化合物蒸氣。 3 ·如申請專利範圍第1項記載之碳氫化合物蒸氣之 回收方法，其中在第2工程中，使用溫水以做爲加熱上述 碳氫化合物蒸氣之一部份被去除之氣體之熱媒體。 4 ·如申請專利範圍第1項記載之碳氫化合物蒸氣之 回收方法，其中在第3工程中，將由第2工程被升溫之氣 體供給於吸著手段，使碳氫化合物蒸氣吸著於吸著劑後， 減壓上述吸著手段內，使淸淨空氣逆流於此吸著手段內， 在此狀態，將碳氫化合物由吸著劑分離之。 5 ·如申請專利範圍第4項記載之碳氫化合物蒸氣之 回收方法，其中在第3工程中，使用複數之吸著手段，將 這些吸著手段交互切換爲吸著處理與分離處理，以進行連 續之處理。 6 ·如申請專利範圍第4項記載之碳氫化合物蒸氣之A8B8C8D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and applying for patents1. A method for recovering hydrocarbon vapors, which is characterized by: cooling the gas containing hydrocarbon vapors by means of cooling to remove the carbon The first process of a part of the hydrogen vapor, and the second process of heating the part of the hydrocarbon vapor removed by heating to raise the temperature, and supplying the heated gas to the (3) The adsorption means for filling the adsorbent. Here, the third process is to adsorb and remove the hydrocarbon vapor. 2. The method for recovering hydrocarbon vapors as described in item 1 of the scope of the patent application, wherein the above-mentioned condensed liquid hydrocarbons are used in the first process, and the cooled liquid hydrocarbons and hydrocarbons are contained The gaseous vapor is contacted to cool the hydrocarbon vapor in the condensed gas. 3. The method for recovering hydrocarbon vapor as described in item 1 of the scope of patent application, wherein in the second project, warm water is used as a heat medium for heating the gas from which a part of the hydrocarbon vapor is removed. 4. The method for recovering hydrocarbon vapors as described in item 1 of the scope of the patent application, wherein in the third process, the gas heated in the second process is supplied to the adsorption means, so that the hydrocarbon vapors are adsorbed to the adsorption After the agent, the inside of the adsorption means is decompressed, and the clean air is allowed to flow countercurrently in the adsorption means. In this state, hydrocarbons are separated from the adsorbent. 5. The method for recovering hydrocarbon vapors as described in item 4 of the scope of the patent application, wherein in the third process, a plurality of adsorption means are used, and these adsorption means are switched to adsorption treatment and separation treatment alternately to perform Continuous processing. 6 ・ As mentioned in the scope of patent application for the hydrocarbon vapor 訂 ▲ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -28- 565468 A8 B8 C8 D8 六、申請專利範圍 回收方法，其中將由第3工程之吸著劑分離之碳氫化合物 與含有第1工程之碳氫化合物蒸氣之氣體混合，以冷卻凝 縮回收之。 7 · —種碳氫化合物蒸氣之回收裝置，其特徵爲具備 :冷卻凝縮含有碳氫化合物蒸氣之氣體，以去除上述碳氫 化合物蒸氣之一部份用之冷卻手段， 及加熱上述碳氫化合物蒸氣之一部份被去除之氣體以 使之升溫用之加熱手段， 及被塡充吸著去除上述被升溫之氣體中之碳氫化合物 蒸氣之吸著劑之吸著手段。 8 ·如申請專利範圍第7項記載之碳氫化合物蒸氣之 回收裝置，其中設置共通之交換單元以做爲供給於上述冷 卻手段之冷卻用熱媒體之供給源以及供給於上述加熱手段 之加熱用熱媒體之供給源。 9 .如申請專利範圍第7項記載之碳氫化合物蒸氣之 回收裝置，其中上述吸著手段爲了交互切換吸著處理與分 離處理以連續處理之故，被設置爲複數個。 (請先閱讀I背面之：^意事項再 I I - 頁: . --線· 經濟部智慧財產局員工消費合作社印製 -29- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Order ▲ This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -28- 565468 A8 B8 C8 D8 VI. Patent application scope recovery method, in which the hydrocarbon separated by the sorbent of the third project The compound is mixed with a gas containing hydrocarbon vapor of the first process, and is recovered by cooling and condensation. 7 · A hydrocarbon vapor recovery device, which is characterized by cooling means for cooling and condensing the gas containing hydrocarbon vapors to remove a part of the hydrocarbon vapors, and heating the hydrocarbon vapors Part of the heating means for removing the gas to increase the temperature, and the absorption means for adsorbing and removing the hydrocarbon vapor in the heated gas. 8 · The hydrocarbon vapor recovery device described in item 7 of the scope of the patent application, wherein a common exchange unit is provided as a supply source of the cooling heat medium supplied to the cooling means and a heating supply provided by the heating means. Source of thermal media. 9. The hydrocarbon vapor recovery device according to item 7 in the scope of the patent application, wherein the adsorption means is provided in plural for the purpose of alternately switching between adsorption processing and separation processing for continuous processing. (Please read the back of I: ^ Issue then II-Page:.-Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-29- This paper size applies to China National Standard (CNS) A4 (210 X 297 Mm)