482752 Λ7 五、發明説明（ 經濟部中央標準局員工消費合作社印製 本發明係製“丙Μ之方法，及可合適地用於該程序 义反應器。更特定言之，本發明係由氣相中高溫氣化丙烯 以製造烯丙基鹵。 烯丙基函及更特定烯丙基氣化物顯示製造表由醇及更特 足表氯醇（環氧氣丙烷）之重要的中間產物，而現在表氯醇 本身為製造環氧樹脂之關鍵化學品。 美國專利說明書號5 5〇4 266揭露製造烯丙基鹵之二階方 法；該方法包括： (a) 供應莫耳比至少2.5:丨且合適地少於5:丨之丙烯和自 進入不斷地攪拌的槽式反應器之内； (b) 在由400至525X：溫度範圍下在不斷攪拌的槽式反應 内讓丙晞和齒素部分反應以部份地轉換； (c) 將流出物從不斷攪拌的槽式反應器進料到管狀反 器，其中在由400至525^溫度範圍下讓反應在塞式流動 繼續；和 (d) 將反應產物從管狀反應器中移除。 不斷攪拌的槽式反應器具有球體、橢圓形或蛋形之 狀。 ’ 美國請准專利號5 367 105說明書揭露製造烯丙基鹵方 其方法包含導入反應器内莫耳比由於3 :1到5:丨範圍之氣 丙烯和氣態氯之實質上平行噴射流；及將反應產物由反 器移除。 上述方法所用之反應器包含圓筒形外裝，其具錐形頂 區及被反轉錐形底部區；其中反應物是注射進入錐形項 素 器 應 中 形 法; 態 應 部 部 --------#1 — (請先閲讀背面之注意事項存填寫本頁) 4- 482752 A7 _ B7 五、發明説明（2 ) 區。 其已發現已知之方法有缺點；其提供較低產率或顯著量 的反應副產物形成，其後來產品造成弄髒。再者已知方法 之擴大規模已發現很困難。 因為烯丙基齒逐漸地變成更有價值；故有動機改善產率 且減少副反應產物之的產生。 由於積極研究的結果，己發現改善之方法，其遭受較少 已知方法之不利點。 因此依本發明由氣態丙晞及氣態自素製造烯丙基商之方 法包含： (a) 由入口噴嘴引導丙烯進入管狀環反應器； (b) 引導氣態自素進入管狀環反應器經過幾組軸向間隔之 徑向放置的入口，其提供在管狀環反應器之壁上； (c) 讓丙婦及卣素反應；及 (d) 由出口將反應流出物由管狀環反應器中移除， 其中在任何反應器體積單元中卣素濃度基於總氣體混合物 為準，保持3質量％以下；且其中丙烯離開入口喷嘴之線 f生氣心速度至少足夠以維持在管狀環反應器中持績的循 環。 / 經濟部中央標準局員工消費合作社印製 --^--------- (請先閱讀背面之注意事項再填寫本頁) 在說明書及申請專利範圍中所謂：".反應器體積單元”用 以參照由反應器的内部表面及二個垂直於液體流經反應器 方向<軸向分隔平面所足義的單元，該單元具厚度小於反 應器的内部直徑。 鹵化作用為放熱反應’且本發明方法一個優點是持績循 -5-482752 Λ7 V. Description of the invention (The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed the method of the present invention to produce the "PM", and it can be suitably used in the procedural reactor. More specifically, the present invention is based on the gas phase Medium-high temperature gasification of propylene to make allyl halides. Allyl and more specific allyl gas shows important intermediates for the production of alcohols and more specifically epichlorohydrin (epoxy propane), but now the table Chlorohydrin itself is a key chemical for the manufacture of epoxy resins. US Patent Specification No. 55044 266 discloses a second-order method for making allyl halides; the method includes: (a) supplying a molar ratio of at least 2.5: and suitably Less than 5: propylene and self-entering into the continuously stirred tank reactor; (b) in the range from 400 to 525X: in the continuously stirred tank reaction, the propane and the tooth element are partially reacted to Partial conversion; (c) feeding the effluent from a continuously stirred tank reactor to a tubular reactor, where the reaction is allowed to continue in a plug flow at a temperature ranging from 400 to 525 °; and (d) the reaction is continued Product is removed from the tubular reactor. The mixed tank reactor has the shape of a sphere, an oval, or an egg. 'US Patent No. 5 367 105 specification discloses the method of manufacturing an allyl halide. The method includes introducing a molar ratio into the reactor because of 3: 1 to 5 : A substantially parallel jet of gaseous propylene and gaseous chlorine in the range; and removing the reaction product from the reactor. The reactor used in the above method includes a cylindrical outer casing with a tapered top region and an inverted cone. Bottom area; where the reactant is injected into the cone-shaped item device should be in the middle shape method; state response department -------- # 1 — (Please read the precautions on the back first and fill in this page) 4- 482752 A7 _ B7 V. Description of the Invention (2) Zone. It has been found to have disadvantages with known methods; it provides lower yields or significant amounts of reaction by-product formation, and its subsequent products cause soiling. Scale-up has been found to be difficult. As allyl teeth gradually become more valuable, there is an incentive to improve yields and reduce the production of side-reaction products. As a result of active research, improved methods have been found that suffer less Disadvantages of known methods. The method for producing an allyl maker from a gaseous propionate and a gaseous autogen according to the present invention includes: (a) introducing propylene into a tubular ring reactor through an inlet nozzle; (b) directing a gaseous autogen into a tubular ring reactor through several groups An axially spaced, radially placed inlet provided on the wall of the tubular ring reactor; (c) allowing the bupropion and hydrazone to react; and (d) removing the reaction effluent from the tubular ring reactor through the outlet Where the concentration of halogen in any reactor volume unit is based on the total gas mixture, which is maintained below 3% by mass; and where the line of propylene leaving the inlet nozzle is at least sufficient to maintain its performance in the tubular ring reactor Recycling. / Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-^ --------- (Please read the precautions on the back before filling out this page) The so-called in the specification and patent application scope: ". "Reactor volume unit" is used to refer to the unit defined by the inner surface of the reactor and two planes perpendicular to the direction of the liquid flowing through the reactor < the axial separation plane. The unit has a thickness smaller than the internal diameter of the reactor. Halogenation is an exothermic reaction 'and one advantage of the method of the present invention is that
482752 A7 B7 五、發明説明（3 ) %挺供整個反應器均勾的溫度分配。而且再循環速率可調 節以改善溫度控制。 依照本發明方法一較優實例再包含： (e) 將步驟（d )中移除之反應流出物導入管狀反應器之入 口端中； (f) 經過幾組軸向間隔之幅射向放置的入口引導氣態卣素 進入管狀反應器内，入口組為提供在管狀反應器壁上；及 讓鹵素及丙烯反應；及 (g) 將反應產物由管狀反應器的出口端移除。 較優卣素氣體為氯氣。 本發明再係反應器，其包括管狀環反應器，其具至少一 入口喷嘴，幾組軸向間隔之徑向放置的入口，其提供在管 狀環反應器壁上，及出口。 本發明現由參照所附圖面之諸例更詳細地描述；其中 圖1 a、1 b及1 C顯示適供用於依照本發明方法之反應器 例三個延長區段示意圖； 圖2表示反應器改善設計之一個經度區段之示意圖；及 圖3表示比圖形la_lc標度更大所繪管狀環反應器部分經 度區段之示意圖。 經濟部中央標準局員工消費合作社印製 :--^-------0 — I (請先閲讀背面之注意事項再填寫本頁) 元組件編號說明 1 反應器 17 入口端 2 管狀環反應器 19 組 3 八口噴嘴 20 入口 4 入口 21 壁 -6- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 482752 A7 B7 五、發明説明（4 5 壁 25 出口端 6 組 30 喷射器 9 出π 35 入口 12 箭頭 37 半頂角 13 反應器體積單元 40 支撐輥 15 反應器 經濟部中央標準局員工消費合作社印製 現參照圖la-1 c。反應器丨包含管狀環反應器2。管狀環 反應器2可具延長的形狀（如圖形1 a所示）；圓形的形狀（如 圖形1 b所不）或橢圓的形狀（如圖形1 c所示）。 管狀環反應器2提供至少一個入口喷嘴3及多數的入口 4 ’其提供在管狀環反應器2之壁5上。入口 4安排成數組 轴向間隔組6 ’且在每組中入口徑向放置，此即沿著管狀 每反應器2之圓周分佈。為清楚緣故計，不是所有的入口 噴嘴且不是所有組皆已參照具參考碼。 管狀環反應器再提供具靠近入口噴嘴3放置之出口9 合適地’出口 9位於管狀環反應器2之下游端；入口噴嘴 的下游。 在一般操作時，丙烯由入口噴嘴3導入管狀環反應 之内’且氣態自素是由多數入口 4導入管狀環反應器 内。反應混合物依箭頭1 2的方向通過管狀環反應器2。 應流出物經出口 9由管狀環反應器2移走；及由此反應流 物傳送到回收設備（未顯示）而由本身已知的方法分離所 的烯丙基卣。反應流出物之剩餘物循環經管狀環反典 2。再循環比（R)定義為再循環反應混合物之量對注 3 器2 2之 反 出 需 器 射噴 (請先閲讀背面之注意事項再填寫本頁) 、1Τ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） 482752 A7 ------- B7 __ 五、發明説明（5 ) 嘴3注射丙烯的量之質量比率。 反應條件選定以致於其中在任何反應器體積單元1 3中 鹵素濃度基於總氣體混合物為準，保持3質量％以下；且 其中丙埽離開入口喷嘴3之線性氣體速度至少足夠以維持 在管狀環反應器2中持續的循環。 丙埽離開入口噴嘴（3 )之線性氣體速度（υ^)必須足夠以 引起： a) 在管狀環反應器每個剖面之平均速度（1^)大於2 〇公尺 /秒’較優大於4 0公尺/秒上方；及 b) 再循環比（R)確定環反應器中最小溫度大於4〇〇〇c ;較 優大於430X：。環反應器中的最大溫度一定低於52〇r，較 優低於500°C下。 適當的再循環比（R)之值大於2且較優大於3。 申请者冒經發現當選定如此條件時，可產生具良好選擇 性之晞丙基卣且較優烯丙基氯化物。由於特為丨，5-己二婦 副反應產物的顯著減少，其為流出物中的重氯醚的主要先 質，故所得烯丙基氯化物染色較少。 經濟部中央標準局員工消費合作社印製 -,-I：-------0! f請先閲讀背面之注意事項再填寫本頁} 合適入口 4之組6的數目在由2到15的範圍，且較優在由 6到1 2的範圍，而且每組内入口 4的數目在由2到8的範 圍。 一個剖面中徑向放置每組函素入口的數目通常在由2到 1 5及較優由4到1 2的範圍。 合適的注射噴嘴3為超過一個，該注射噴嘴是沿著管狀 環反應器2軸向隔開。為決定再循環比，需指定由所有注 -8- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐) ' --- A7 ______ B7_____ 五、發明説明（6 ) 射噴嘴所得丙烯總量。 現參考圖2。於此圖面所顯示反應器1再包含管狀反應 备15 ’其具入口端17，其與管狀環反應器2中出口 9流 通。 所提供管狀反應器1 5具幾組1 9軸向間隔之徑向放置的 入口 20 ’其提供在管狀反應器15壁21上。 管狀反應器1 5具出口端2 5以將反應產物由反應器1中移 除。 在通¥操作時’反應流出物由出口 9移走導入管狀反應 器15的入口端17之内，氣態_素由提供在管狀反應器壁 上軸向隔開之徑向放置的入口 2 〇組1 9，導入管狀反應器 1 5内。讓_素與未反應丙烯反應，而反應產物由管狀反 應器1 5的出口端2 5移走，及由此反應產物經過到回收設 備（未顯示）以本身已知的方法分離所需的烯丙基鹵。 現參照圖3。此設計所用入口噴嘴為噴射器3 〇，且丙烯 進料的部分導入經輔助的入口 3 5，所以再循環比可經由 調節丙烯供應經噴射器3 〇及輔助入口 3 5之數量而減少。 如圖3所示，噴射器3 〇的尾端部分逐漸變小，且半頂角3 7 經濟部中央標準局員工消費合作社印製 — II ——— (請先閲讀背面之注意事項再填寫本頁) 約為2 。此外，噴射器3 0的尾端由支撐輥4 〇支撐，其合 適地為3個。 如果依照本發明方法一較優實例，環反應器及互連之管 狀反應器之組合，使用導入管狀環反應器之内自素，相^ 於導入管狀環反應器及管狀反應器兩者之内總鹵素而士， 其莫耳比介於由6 0到100%的範圍内，且更優由7 〇到 -9 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 482752 A7 ________ B7_ 五、發明説明（7 ) 90%。 卣素進料且較優氯氣進料的入口溫度在由50到150°C及 較優由6 0到π 0 °C及更優由8 〇到110 °C的範圍内，但經由 每個個別入口導入函素的溫度可能是相同或不同。 導入管狀環反應器之内卣素且較優氯氣的溫度較優為約 相同’且導入可選擇的管狀反應器氣態鹵素溫度可能也具 相同的值，雖然齒素的個別溫度，在一方面導入環反應器 之内及另一方面導入可選擇的管狀反應器之内，可能是不 同的。導入之丙烯將會具溫度在由2〇〇到4〇〇°C，及較優由 230到36(TC的範圍内。不同的反應溫度可施用在環反應器 的不同剖面及個別的可選擇的管狀反應器及尤其在管狀反 應器區分不同區域之施用溫度。 典型地環反應器中滯留時間（r環）平均由〇 5秒到3秒，且 管狀反應器（r *)中滞留時間由0.2秒到1秒。 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 大體上，管狀環反應器的内部直徑（單位公尺）下式決 足··環直徑=A*(R/ τ環）*(U2丙烯/U3環）*d2，其中A是依反 應器材料的表面性質而定之完全根據經驗值（_); R為再循 %比,τ環為環反應器（單位秒）中滯留時間；為丙烯 離開賣嘴之線性速度（單位公尺/秒）；U環為管狀環反應器 .中之線性速度（單位公尺/秒）；及4為丙烯喷嘴的内部直徑 (單位公尺）。 在實際情況下，A將具由2 〇到4 0及較優由2 5到3 5範圍 的值。 沿著管狀環反應器的入口組數目為選自上述的極端重畏 -10- 本纸張尺i適用中國國家標準（CNS ) A4規格（21〇 X297公^------ 482752 A7 B7 五、發明説明（8 的濃度需求。故較優地將每組放置在沿著管狀環反應器相 等的距離。 管狀反應器的内部直徑為選定以使管狀反應器中線性速 度介於2 0至8 0公尺/秒之間。入口組數目及其位置之測定 決定方式同樣於管狀環反應器之方式。 依照較優實例，使用環反應器及管狀反應器的組合，環 反應器的體積為較大於管狀反應器的體積。 其將會瞭解到本發明也係特定的反應器組件，其中可進 行上述之方法。 其將會暸解到本管狀反應器更優組成包含經出口連接至 環反應器之直管，然而，其他的選擇，亦可應用其中直管 狀反應器經由一個或多彎管部分連接到環反應器。 更優環反應器的内部直徑相對於管狀反應器内部直徑之 比率介於由4:1到3:2的範園，且管狀環反應器的體積=對 於^狀反應器的體積之比率在由6到9的範圍。 如圖2所述反應器組件中，該環反應器外部最大長度相 對於構成環反應器之管直徑的比率介於由3 〇到5 〇的範 圍，同時該管狀環反應器外部最大寬度相對於直 卜^ 介於由3到5的範圍。 ^匕率 經濟部中央標準局員工消費合作社印製 ： ： -- (請先閲讀背面之注意事項再填寫本頁) 較優管狀環反應器的外部最大長度比上環反應器的 直徑之比率介於由3 5到4 5的範圍。 口 本發明由下諸例再舉例說明，然而其範圍沒有 實例。 匕 本紙張尺度適财關家縣（CNS ) -11 482752 A7 B7 五、發明説明（9 ) 例1 依照圖2的反應器中，丙婦下列條件之下以氯轉化： 丙烯預先加熱（°C ) : 340 氯預先加熱（°C) : 70 丙婦/氣吴耳比· 4.2 反應器出口溫度（°C ) ·· 505 丙烯進料速率（公斤/小時）： 6300 氯進料速率（公斤/小時）； 2536 反應壓力（絕對壓力（巴））： 3.2 環反應器中的滯留時間，r環(s) : 1.8 管狀反應器中的滯留時間，h(s) : 0.2 丙烯噴射器之線性速度，U㈣（公尺/秒）： 355 環反應器中的氣體速度，U環（公尺/秒）： 40 環反應器的内部直徑，D環（公尺）： 〇·3 管狀反應器的内部直徑，D* (公尺）·· 〇·15 丙烯喷射器的直徑，d (公尺）： 0.055 環反應器中的氯氣入口組的數目： 7 管狀反應器中的氯入口組的數目： 3 再循環比： 3 基於丙烯轉換莫爾數之產率（莫耳％): 烯丙組氯化物： 89.37 經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再填寫本頁) 2-鼠丙婦· 2.81 1，2-二氯丙烷： 1.38 順式-1，3 -二氣丙婦· 1.95 反式—·鼠丙婦· 1.76 其他： 2.73 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）482752 A7 B7 V. Description of the invention (3)% It is used for temperature distribution of the whole reactor. And the recirculation rate can be adjusted to improve temperature control. A preferred example of the method according to the present invention further comprises: (e) introducing the reaction effluent removed in step (d) into the inlet end of the tubular reactor; (f) passing several sets of axially spaced radiation towards the placed The inlet guides gaseous halogen into the tubular reactor, the inlet group is provided on the wall of the tubular reactor; and the halogen and propylene are reacted; and (g) the reaction product is removed from the outlet end of the tubular reactor. The preferred gasein is chlorine. The present invention further relates to a reactor comprising a tubular ring reactor having at least one inlet nozzle, several sets of axially spaced radially placed inlets, provided on the wall of the tubular ring reactor, and an outlet. The present invention is now described in more detail by reference to the examples of the attached drawings; wherein Figures 1a, 1b and 1C show schematic diagrams of three extended sections of a reactor example suitable for use in the method according to the invention; Figure 2 shows the reaction A schematic diagram of a longitude section of the improved design of the reactor; and FIG. 3 shows a schematic diagram of the longitude section of the tubular ring reactor portion drawn larger than the graph la_lc scale. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs:-^ ------- 0 — I (Please read the precautions on the back before filling out this page) Description of component number 1 reactor 17 inlet 2 tubular ring Reactor 19 Group 3 Eight-nozzle 20 Inlet 4 Inlet 21 Wall -6- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 482752 A7 B7 V. Description of the invention (4 5 wall 25 outlet end 6 groups 30 Ejector 9 Out π 35 Inlet 12 Arrow 37 Half-corner angle 13 Reactor volume unit 40 Support roll 15 Reactor printed by the Ministry of Economic Affairs Central Standards Bureau ’s Consumer Cooperatives Refer to Figure la-1c. The reactor contains a tubular ring reaction Reactor 2. The tubular ring reactor 2 can have an extended shape (as shown in Figure 1 a); a circular shape (as shown in Figure 1 b) or an oval shape (as shown in Figure 1 c). The reactor 2 provides at least one inlet nozzle 3 and a plurality of inlets 4 'which are provided on the wall 5 of the tubular ring reactor 2. The inlets 4 are arranged in arrays of axially spaced groups 6' and the inlets are placed radially in each group, ie Along the circumference of each reactor tube 2 For the sake of clarity, not all inlet nozzles and not all groups have been referred to with reference codes. The tubular ring reactor is further provided with an outlet 9 placed close to the inlet nozzle 3, suitably 'outlet 9 is located in the tubular ring reactor 2 Downstream end; downstream of the inlet nozzle. In normal operation, propylene is introduced into the tubular ring reactor through the inlet nozzle 3 and the gaseous autogen is introduced into the tubular ring reactor through the majority of the inlet 4. The reaction mixture passes in the direction of the arrow 12 Tubular ring reactor 2. The effluent should be removed from the tubular ring reactor 2 through the outlet 9; and the reaction stream is then transferred to a recovery device (not shown) and the allyl hydrazone is separated by a method known per se. The remainder of the reaction effluent is circulated through the tubular ring anti-code 2. Recycling ratio (R) is defined as the amount of the recirculated reaction mixture to the injection nozzle of the injector 3 and 2 (please read the precautions on the back first) (Fill in this page), 1T This paper size is applicable to China National Standard (CNS) A4 specification (210X29 * 7mm) 482752 A7 ------- B7 __ 5. Description of the invention (5) The amount of propylene injected in the mouth 3 Mass ratio The reaction conditions are selected so that the halogen concentration in any reactor volume unit 13 is based on the total gas mixture, which is maintained below 3% by mass; and where the linear gas velocity of the tritium leaving the inlet nozzle 3 is at least sufficient to maintain the tubular ring Continued circulation in reactor 2. The linear gas velocity (υ ^) of the tritium leaving the inlet nozzle (3) must be sufficient to cause: a) the average velocity (1 ^) in each section of the tubular ring reactor is greater than 2 0 cm Feet / second 'is more preferably above 40 meters / second; and b) the recycle ratio (R) determines that the minimum temperature in the loop reactor is greater than 4000c; more preferably, it is greater than 430X :. The maximum temperature in the loop reactor must be below 52 ° C, preferably below 500 ° C. A suitable recycling ratio (R) has a value greater than 2 and more preferably greater than 3. Applicants have discovered that when such conditions are selected, a well-selected stilbene hydrazone and a more preferred allyl chloride are produced. Due to the significant reduction of the side reaction products, especially hexamethylene dichloride, which is the main precursor of dichloroether in the effluent, the resulting allyl chloride is less stained. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-,-I: ------- 0! F Please read the notes on the back before filling out this page} The number of groups 6 suitable for entrance 4 is from 2 to 15 The range is preferably from 6 to 12 and the number of entrances 4 in each group is from 2 to 8. The number of radial element entrances for each group in a profile is usually in the range from 2 to 15 and more preferably from 4 to 12. Suitable injection nozzles 3 are more than one, which are axially spaced along the tubular ring reactor 2. In order to determine the recycling ratio, it is necessary to specify that all papers are used in accordance with the Chinese National Standard (CNS) A4 size (210X 297 mm) for this paper size. Total. Reference is now made to FIG. 2. The reactor 1 shown in this figure further comprises a tubular reaction device 15 'which has an inlet end 17 which communicates with an outlet 9 in the tubular ring reactor 2. The tubular reactor 15 is provided with several groups of 19 axially spaced radially placed inlets 20 ' which are provided on the wall 21 of the tubular reactor 15. The tubular reactor 15 has an outlet end 25 to remove the reaction product from the reactor 1. During the operation, the reaction effluent is removed from the outlet 9 and introduced into the inlet end 17 of the tubular reactor 15, and the gaseous element is provided by a radially placed inlet 20 provided axially spaced on the wall of the tubular reactor. 19, introduced into the tubular reactor 15. The element is allowed to react with unreacted propylene, and the reaction product is removed from the outlet end 25 of the tubular reactor 15 and the reaction product is then passed to a recovery device (not shown) to separate the desired olefin by a method known per se Propyl halide. Reference is now made to FIG. 3. The inlet nozzle used in this design is ejector 30, and the part of the propylene feed is introduced into auxiliary inlet 35, so the recycling ratio can be reduced by adjusting the number of propylene supply through ejector 30 and auxiliary inlet 35. As shown in Figure 3, the trailing end of the ejector 3 is gradually smaller, and the half-top angle is 37. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs — II ——— (Please read the precautions on the back before filling in this Page) is about 2. In addition, the trailing end of the ejector 30 is supported by the supporting roller 40, which is suitably three. According to a preferred example of the method of the present invention, the combination of the ring reactor and the interconnected tubular reactors uses the internal element introduced into the tubular ring reactor, which is equivalent to the introduction into both the tubular ring reactor and the tubular reactor. For total halogen, its molar ratio is in the range of 60 to 100%, and more preferably in the range of 70 to -9.-This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 482752 A7 ________ B7_ V. Description of the invention (7) 90%. The inlet temperature of halogen feed and better chlorine feed is in the range from 50 to 150 ° C and more preferably from 60 to π 0 ° C and more preferably from 80 to 110 ° C. The inlet lead-in temperature may be the same or different. Introduce the internal halogen and the preferred temperature of the chlorine gas in the tubular loop reactor is about the same, and the optional halogen gas temperature in the optional tubular reactor may also have the same value, although the individual temperature of the tooth element is introduced on the one hand The inside of the loop reactor and the introduction into the optional tubular reactor on the other hand may be different. The propylene introduced will have a temperature in the range from 2000 to 400 ° C, and preferably from 230 to 36 ° C. Different reaction temperatures can be applied to different sections of the loop reactor and individual options The tubular reactor and the application temperature in different regions, especially in the tubular reactor. Typically, the residence time (r-ring) in a ring reactor ranges from 0.05 to 3 seconds, and the residence time in a tubular reactor (r *) is from 0.2 seconds to 1 second. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Generally, the internal diameter (unit meter) of the tubular ring reactor is determined by the following formula ... Ring diameter = A * (R / τ ring) * (U2 propylene / U3 ring) * d2, where A is determined by the surface properties of the reactor material and is completely based on empirical values (_); R is the percentage of recirculation, τ The ring is the residence time in the ring reactor (in seconds); the linear velocity (in meters / second) of the propylene leaving the selling nozzle; the U ring is the linear velocity (in meters / second) in the tubular ring reactor; and 4 is the internal diameter of the acrylic nozzle (in meters). In practice, A will have 2 Values ranging from 40 to 40 and more preferably from 25 to 35. The number of inlet groups along the tubular ring reactor is selected from the above extreme weights -10- This paper rule applies to Chinese National Standard (CNS) A4 Specifications (21〇X297) ^ -------- 482752 A7 B7 V. Description of the invention (8 concentration requirements. Therefore, it is better to place each group at an equal distance along the tubular ring reactor. The inside of the tubular reactor The diameter is selected so that the linear velocity in the tubular reactor is between 20 and 80 meters / second. The number of inlet groups and their positions are determined in the same way as the tubular ring reactor. According to a better example, use The combination of a ring reactor and a tubular reactor, the volume of the ring reactor is larger than the volume of the tubular reactor. It will be understood that the present invention is also a specific reactor component in which the above method can be performed. It will be understood The more optimal composition of this tubular reactor includes straight tubes connected to the loop reactor via an outlet, however, other options are also applicable where the straight tubular reactor is connected to the loop reactor via one or more elbow sections. Inside of the reactor The ratio of the diameter to the internal diameter of the tubular reactor is in the range from 4: 1 to 3: 2, and the ratio of the volume of the tubular ring reactor to the volume of the reactor is in the range from 6 to 9. In the reactor assembly shown in FIG. 2, the ratio of the maximum outer length of the ring reactor to the diameter of the tube constituting the ring reactor is in a range from 30 to 50, and the maximum outer width of the tubular ring reactor is ^ ^ The range is from 3 to 5. ^ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs:: (Please read the precautions on the back before filling this page) The outside of the better tubular ring reactor is the largest The ratio of the length to the diameter of the upper loop reactor is in the range from 35 to 45. The present invention is illustrated by the following examples, but its scope is not exemplified. The paper size is suitable for Guancai County (CNS) -11 482752 A7 B7 V. Description of the invention (9) Example 1 In the reactor according to Fig. 2, the woman was converted with chlorine under the following conditions: Propylene was preheated (° C ): 340 Chlorine preheating (° C): 70 C / w / w · 4.2 reactor outlet temperature (° C) · 505 propylene feed rate (kg / h): 6300 chlorine feed rate (kg / h Hours); 2536 reaction pressure (absolute pressure (bar)): 3.2 residence time in a loop reactor, r-ring (s): 1.8 residence time in a tubular reactor, h (s): 0.2 linear velocity of a propylene ejector , U㈣ (meter / second): Gas velocity in 355 ring reactor, U ring (meter / second): 40 ring reactor internal diameter, D ring (meter): 0.3 internal tube reactor Diameter, D * (meters) ··· 15 Diameter of propylene injector, d (meters): 0.055 Number of chlorine gas inlet groups in a loop reactor: 7 Number of chlorine gas inlet groups in a tubular reactor: 3 Recycling ratio: 3 Yield based on moles of propylene conversion (mole%): Allyl chloride: 89.37 Economy Printed by the Consumer Standards Cooperative of the Central Bureau of Standards (please read the precautions on the back before filling out this page) 2-Rhythmine · 2.81 1,2-Dichloropropane: 1.38 Cis-1,3-Digasmine · 1.95 Trans- · Rabine Fu · 1.76 Others: 2.73 -12- This paper size applies to China National Standard (CNS) A4 (210X297 mm)