474905 經濟部中央標準局員工消費合作社印製474905 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs
五、發明説明（i ) 工業上，氯乙烯（K下簡稱VC)係在高壓及450至600t 溫度下，藉將1,2-二氯乙烷（以下簡稱EDC)加以熱裂煉而 製得。在此製造過程中，進給EDC,約有40至65¾經裂解成 為VC及氯化氫。熱裂煉時所形成之副產品，其沸點有高於 或低於EDC者。所Μ必須蒸餾實施多步驟分離工作。 熱裂煉之氣體產物（裂解氣體）首先通過一過濾器Κ除 去較粗之焦碳顆粒，經冷凝後再通入第一蒸餾塔（氯化氫 塔），其中氯化氫經蒸餾出去成為塔頂產物。塔底部分包 括未反應之EDC、低-及高-沸點副產品及較细之焦碳顆粒。 該等焦碳顆粒尤其影響苯之清除工作，所Μ目前塔底 產物之複雜分_工作及進給至苯清除步驟之部分流動體之 純化工作均甚需要。該分餾及部分純化工作最好藉急驟蒸 發來完成。 德國專利DE-A 40 33 047曾揭示一種方法用以清除： 製備VC過程中，VC及氯化氫經分離之後，EDC内再生之苯， VC塔塔底之EDC係經分為：清除高沸點物質而鈍化之生成物 流動體及未經鈍化之生成物流動體，在有金属鐵存在及溫 度30至851C之情況下，用氯將該經鈍化之生成物流動體加 以處理，並將該生成物流動體與未經純化之生成物流動體 再度結合，再於進一步純化步驟内，連同EDC自高沸點物 質中分離出來。該方法經改良後，採用之催化劑是型 氧化鋁（德國專利DE-A 41 29 391)。 德國專利DE-A 41 39 632中亦曾揭示一種方法用以清 除：製備VC過程中，VC及氯化氫之分離操作之下游，EDC -II - - — - I I H - I n _ I τ \ 、τ (請先閲讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準（〇~$)六4規格（210；<297公1) 474905 經濟部中央標準局員工消費合作社印製 五、發明説明（2 ) 内再生之苯。該方法之特徵是：將來自VC塔塔底、經污染 之EDC分成不含高沸點物質（沸點>83.71，760公厘汞柱） 之生成物流動體I及含有高沸點物質（沸點>83.7t：, 760 公厘汞柱）之生成物流動體在有金属鐵存在及溫度30 至8510之情況下，用氯將生成物流動體I加以處理，使經 處理之生成物流動體I與生成物流動體E相結合，並在30 至85C溫度下用氯共同處理結合後之流動體，再於一蒸餾 區内，將純化之EDC自該生成物流動體内分離出來。 德國專利DE-A 41 32 761中曾掲示一種用K精製裂解 氣體之方法，該裂解氣體係在溫度480至540t!及壓力15至 25巴之情況下EDC熱裂煉生成VC時製得，（假若適當）在一 熱回收區，經冷卻至180至2801C,並在此溫度下將其送入 一驟冷區，其中藉冷凝之裂解氣體加以冷卻及脫餾，該方 法之特徵是：a)80至99¾重量比之冷卻裂解氣體呈氣態塔 頂產物除去及1至20¾重量比之冷卻裂解氣體圼驟冷區液態 塔底產物除去，b)驟冷區塔底產物中之焦碳係加以磨碎， c) 在此案例中製得之分散液係在一脫餾區分離為一蒸餾液 及一塔底產物，由該方法產生之塔底產物則予以排出去及 d) 脫餾區之蒸餾液係與冷凝後之驟冷區氣態塔頂產物相結 合。最好3至6%重量比係呈驟冷區塔底產物除去。 經發琨下列驟冷操作之方式適於大幅簡化苯之氯化作 用：假若EDC熱裂煉之氣態產物經冷卻至較窄較低之溫度 範圍約150至180t!，尤以160至170t更佳，產物流動體之 分餾及該等產物流動體之一之鈍化可Μ省略，所M,在此 -4 * (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 ) Λ4規格（210X 297公;^ ) 474905 經濟部中央標準局員工消費合作社印製 Λ7 ___ B7 五、發明説明（3 ) 冷凝步驟内，僅一小部分EDC，連同高沸點分餾物及形成 之焦碳實施冷凝。所Μ大部分未反應之EDC係連同VC產物 及氯化氫送至蒸餾精製塔，首先是氯化氫，在下一步驟内 是VC,藉蒸餾作用次第由EDC中分離出來。之後，無需純 化，殘留之EDC可送至另一工廠將苯除去，其中依照德國 專利DE-A 41 29 391所述之方法，採用-氧化鋁較為有 利。 為使EDC及VC中苯及其副產品之含量夠低，通常僅一 部分EDC經歷苯之氯化作用即可。但依照本發明，一件如 控制閥之簡單器具即可將其分餾成為若干部分流動體。 依照本發明，低於7¾(尤以低於5¾更佳）之EDC可加Μ 冷凝，所以僅少部分含焦碳冷凝液必須分別加以精製。再 者，在習知苯氯化之方法中所必需之急驟蒸發操作可以省 略，因此本發明之方法大幅簡化。 茲藉下列實驗例將本發明加以更詳盡之說明。 實驗例： 利用驟冷區之裂解氣體冷凝液將EDC熱裂煉產生之裂 解氣體冷卻至約160至1701C, 4%之裂解氣體得以凝結為液 體。所有焦碳均進入該冷凝液內。將該焦碳除去並分別加 以精製。 將約96¾未凝結之氣態裂解氣體自塔頂送至驟冷區並 再送至一中間冷凝器内而凝結為液體。同樣地將該冷凝液 送至氯化氫塔。在隨後氯化氫塔及VC塔之蒸餾過程中，塔 底產物中均不含焦碳。經冷卻至約30至50C之後，藉助於 -5 - 本紙張尺度適用中國國家標準（CNS ) Λ4規格（210Χ297公釐） n I...... I i— - 1 .....I 1 i^i I-良 —I- I—8 .^1 1^1 —1· τ» β 言 (請先閱讀背面之注意事項再填寫本頁) 474905 Λ7 五、發明説明（4 ) 一控制閥，VC塔之塔底產物分為兩股部分流動體：約8噸 /小時通入苯氯化反應器，約20噸/小時邁過苯氯化反應器 並與該反應器之產物相合併。未經冷卻，將該合併之產物 流動體送至氯丁二烯氯化反應器，並由該處送至高沸點塔。 因此，在本發明之程序中，有闞急驟蒸發及過濾之工 廠設備則可省去。 ---------'^-- (請先閱讀背面之注意事項再填寫本頁)V. Description of the Invention (i) Industrially, vinyl chloride (hereinafter referred to as VC) is obtained by thermal cracking of 1,2-dichloroethane (hereinafter referred to as EDC) at a high pressure and a temperature of 450 to 600t. . During this manufacturing process, about 40 to 65¾ of EDC is fed into VC and hydrogen chloride. The by-products formed during thermal cracking have boiling points above or below EDC. All M must be distilled to perform multi-step separation work. The pyrolysis gas product (cracked gas) is first passed through a filter K to remove coarser coke particles, and after condensing, it is passed to the first distillation tower (hydrogen chloride tower), where hydrogen chloride is distilled out to become the overhead product. The bottom part of the column includes unreacted EDC, low- and high-boiling by-products, and finer coke particles. These coke particles especially affect the removal of benzene, so the complicated separation of the bottom product and the purification of some of the fluids fed to the benzene removal step are all needed. This fractionation and partial purification is best accomplished by flash evaporation. German patent DE-A 40 33 047 has disclosed a method for removing: in the process of preparing VC, after the VC and hydrogen chloride are separated, the benzene is regenerated in the EDC, and the EDC system at the bottom of the VC tower is divided into: Passivated product fluids and unpassivated product fluids are treated with chlorine in the presence of metallic iron and the temperature is 30 to 851C, and the product is flowed. The body is recombined with the unpurified product mobile body, and is separated from the high boiling point material together with EDC in a further purification step. After the method is improved, the catalyst used is alumina (German Patent DE-A 41 29 391). German patent DE-A 41 39 632 has also disclosed a method for removing: during the preparation of VC, downstream of the separation operation of VC and hydrogen chloride, EDC -II----IIH-I n _ I τ \, τ ( Please read the notes on the back before filling in this page) This paper size is applicable to the Chinese national standard (0 ~ $) 6 4 specifications (210; < 297 public 1) 474905 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (2) Regenerated benzene. The method is characterized in that the contaminated EDC from the bottom of the VC tower is divided into a product fluid I containing no high boiling point substances (boiling point > 83.71,760 mmHg) and high boiling point substances (boiling point > 83.7t :, 760 mmHg) in the presence of metallic iron and a temperature of 30 to 8510, the product fluid I is treated with chlorine, so that the treated product fluid I and The product fluid E is combined, and the combined fluid is co-treated with chlorine at a temperature of 30 to 85C, and the purified EDC is separated from the product fluid in a distillation zone. German patent DE-A 41 32 761 has shown a method for refining cracked gas using K. The cracked gas system is produced when EDC is thermally cracked to produce VC at a temperature of 480 to 540 t! And a pressure of 15 to 25 bar. If appropriate) in a heat recovery zone, cooled to 180 to 2801C, and sent to a quench zone at this temperature, where the condensed cracked gas is used to cool and dedistillate, the method is characterized by: a) 80 to 99¾ weight ratio of the cooled cracked gas is removed as a gaseous overhead product and 1 to 20¾ weight ratio of the cooled cracked gas is removed from the liquid bottom product in the quench zone; b) coke in the bottom product of the quench zone is ground Crushed, c) the dispersion obtained in this case is separated into a distillation liquid and a bottom product in a destillation zone, and the bottom product produced by this method is discharged and d) the distillation in the de distillation zone The liquid system is combined with the gaseous overhead product from the quench zone after condensation. Preferably 3 to 6% by weight are removed from the bottom of the column in the quench zone. The following quenching operation methods are suitable to greatly simplify the chlorination of benzene: If the gaseous products of EDC thermal cracking are cooled to a narrower and lower temperature range of about 150 to 180t !, especially 160 to 170t is better The fractionation of the product fluid and the passivation of one of these product fluids can be omitted, so here-4 * (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) Λ4 specification (210X 297 males; ^) 474905 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Λ7 ___ B7 V. Description of the invention (3) In the condensation step, only a small part of the EDC, together with the high boiling point fraction and the coke formed The carbon is condensed. Most of the unreacted EDC is sent to the distillation refining column together with the VC product and hydrogen chloride. The first is hydrogen chloride, and the next step is VC, which is separated from the EDC by distillation. After that, without purification, the residual EDC can be sent to another plant to remove benzene. Among them, according to the method described in German Patent DE-A 41 29 391, the use of alumina is more advantageous. In order to keep the content of benzene and its by-products low in EDC and VC, only a part of EDC usually undergoes chlorination of benzene. However, according to the present invention, a simple device such as a control valve can be fractionated into a plurality of partial fluids. According to the present invention, EDCs below 7¾ (and more preferably below 5¾) can be condensed by adding M, so only a small part of the coke-containing condensate must be refined separately. Furthermore, the flash evaporation operation necessary in the conventional method for chlorinating benzene can be omitted, and therefore the method of the present invention is greatly simplified. The following experimental examples are used to explain the present invention in more detail. Experimental example: The cracking gas condensate in the quench zone was used to cool the cracking gas produced by EDC thermal cracking to about 160 to 1701C, and 4% of the cracking gas was condensed into a liquid. All coke enters the condensate. This coke was removed and purified separately. About 96¾ of uncondensed gaseous cracked gas was sent from the top of the tower to the quench zone and then to an intermediate condenser to condense into a liquid. This condensate was similarly sent to a hydrogen chloride tower. During the subsequent distillation of the hydrogen chloride column and the VC column, coke was not contained in the bottom product. After cooling to about 30 to 50C, with the help of -5-This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) n I ...... I i—-1 ..... I 1 i ^ i I- 良 —I- I—8. ^ 1 1 ^ 1 —1 · τ »β (please read the precautions on the back before filling this page) 474905 Λ7 V. Description of the invention (4) One control Valve, the bottom product of the VC tower is divided into two partial fluids: about 8 tons / hour passes into the benzene chlorination reactor, and about 20 tons / hour passes through the benzene chlorination reactor and is combined with the product of the reactor . Without cooling, the combined product flow is sent to a chloroprene chlorination reactor and from there to a high boiling point column. Therefore, in the process of the present invention, factory equipment with rapid evaporation and filtration can be omitted. --------- '^-(Please read the notes on the back before filling this page)