1. 聚丙(bing)烯工藝的技術發展

  聚(ju)丙烯（Polypropylene，PP）是以丙烯為單體(ti)經聚(ju)合反(fan)應而生成的聚(ju)合樹(shu)脂。已經成為我國經濟建設(she)中不可缺(que)少的材料(liao)(liao)(liao)(liao)。具體(ti)應用(yong)(yong)在包裝材料(liao)(liao)(liao)(liao)、服裝用(yong)(yong)料(liao)(liao)(liao)(liao)、產業(ye)用(yong)(yong)料(liao)(liao)(liao)(liao)、過濾用(yong)(yong)料(liao)(liao)(liao)(liao)、衛生用(yong)(yong)料(liao)(liao)(liao)(liao)和煙用(yong)(yong)絲束等(deng)。

  四(si)十(shi)多年來，聚丙烯(xi)的催化(hua)劑(ji)不斷開發，不斷改性，尤其是近(jin)二十(shi)年來，其技(ji)術一次又一次飛躍(yue)式的進步，極大地簡化(hua)了聚丙烯(xi)的工藝流程，使裝置(zhi)的投資(zi)和生產(chan)成本降到很(hen)低的水(shui)平。

  聚丙烯常用(yong)工(gong)藝方(fang)法包括淤(yu)漿法工(gong)藝和本體(ti)法工(gong)藝。

  ①. 淤(yu)(yu)漿(jiang)法工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)（Slurry Process）又稱漿(jiang)液法或溶劑(ji)法工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)，是世界(jie)上最(zui)早用于(yu)生(sheng)(sheng)(sheng)產(chan)(chan)聚(ju)丙烯(xi)的(de)(de)(de)(de)工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)技術。從1957年(nian)第(di)一套(tao)工(gong)(gong)(gong)(gong)(gong)(gong)業化(hua)裝(zhuang)置到現在一直是最(zui)主要(yao)(yao)的(de)(de)(de)(de)聚(ju)丙烯(xi)生(sheng)(sheng)(sheng)產(chan)(chan)工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)。典型工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)主要(yao)(yao)包括意(yi)大利 Montedison 工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)、美國(guo)Hercules 工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)、日(ri)本三井(jing)東(dong)壓化(hua)學工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)、美國(guo)Amoco 工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)、日(ri)本三井(jing)油化(hua)工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)以及索維爾工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)等(deng)。這些工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)的(de)(de)(de)(de)開發都基于(yu)當時(shi)的(de)(de)(de)(de)第(di)一代催(cui)化(hua)劑(ji)，采用立式(shi)攪拌釜反(fan)應(ying)器，需要(yao)(yao)脫(tuo)(tuo)灰和(he)脫(tuo)(tuo)無(wu)規(gui)(gui)物，因采用的(de)(de)(de)(de)溶劑(ji)不(bu)(bu)同，工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)流程和(he)操作(zuo)條件有所不(bu)(bu)同。近(jin)年(nian)來，傳統的(de)(de)(de)(de)淤(yu)(yu)漿(jiang)法工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)在生(sheng)(sheng)(sheng)產(chan)(chan)中的(de)(de)(de)(de)比例(li)明顯減少(shao)，保留的(de)(de)(de)(de)淤(yu)(yu)漿(jiang)產(chan)(chan)品主要(yao)(yao)用于(yu)一些高價值領域，如特種BOPP薄(bo)膜、高相對(dui)分子質(zhi)量吹塑(su)膜以及高強度管材等(deng)。近(jin)年(nian)來，人們(men)對(dui)該方法進行(xing)了改進，改進后的(de)(de)(de)(de)淤(yu)(yu)漿(jiang)法生(sheng)(sheng)(sheng)產(chan)(chan)工(gong)(gong)(gong)(gong)(gong)(gong)藝(yi)(yi)使用高活性(xing)的(de)(de)(de)(de)第(di)二(er)代催(cui)化(hua)劑(ji)，可(ke)刪除(chu)催(cui)化(hua)劑(ji)脫(tuo)(tuo)灰步驟(zou)，能(neng)減少(shao)無(wu)規(gui)(gui)聚(ju)合物的(de)(de)(de)(de)產(chan)(chan)生(sheng)(sheng)(sheng)，可(ke)用于(yu)生(sheng)(sheng)(sheng)產(chan)(chan)均(jun)聚(ju)物、無(wu)規(gui)(gui)共(gong)聚(ju)物和(he)抗沖共(gong)聚(ju)物產(chan)(chan)品等(deng)。目(mu)前世界(jie)淤(yu)(yu)漿(jiang)法PP的(de)(de)(de)(de)生(sheng)(sheng)(sheng)產(chan)(chan)能(neng)力約占全球PP總生(sheng)(sheng)(sheng)產(chan)(chan)能(neng)力的(de)(de)(de)(de)13％。

  ②. 本(ben)(ben)體法工藝(yi)的(de)(de)(de)研(yan)究開發(fa)始于20世紀60年代，1964年美(mei)國(guo)Dart公(gong)司采用(yong)釜式反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)建成(cheng)了世界上(shang)第一(yi)套(tao)工業(ye)(ye)化(hua)(hua)本(ben)(ben)體法聚(ju)(ju)丙(bing)(bing)(bing)烯(xi)生(sheng)(sheng)產(chan)(chan)裝(zhuang)置。1970年以后(hou)，日本(ben)(ben)住(zhu)友、Phillips、美(mei)國(guo)EI Psao等公(gong)司都實現了液相(xiang)本(ben)(ben)體聚(ju)(ju)丙(bing)(bing)(bing)烯(xi)工藝(yi)的(de)(de)(de)工業(ye)(ye)化(hua)(hua)生(sheng)(sheng)產(chan)(chan)。與采用(yong)溶(rong)劑(ji)的(de)(de)(de)漿液法相(xiang)比，采用(yong)液相(xiang)丙(bing)(bing)(bing)烯(xi)本(ben)(ben)體法進行聚(ju)(ju)合(he)具有(you)不(bu)使(shi)(shi)用(yong)惰性溶(rong)劑(ji)，反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)系統(tong)內單體濃度高(gao)(gao)，聚(ju)(ju)合(he)速率快，催(cui)化(hua)(hua)劑(ji)活性高(gao)(gao)，聚(ju)(ju)合(he)反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)轉化(hua)(hua)率高(gao)(gao)，反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)的(de)(de)(de)時空生(sheng)(sheng)產(chan)(chan)能(neng)(neng)力更大(da)，能(neng)(neng)耗低，工藝(yi)流程簡(jian)(jian)單，設備少(shao)，生(sheng)(sheng)產(chan)(chan)成(cheng)本(ben)(ben)低，“三廢”量(liang)(liang)少(shao)；容易除(chu)(chu)去聚(ju)(ju)合(he)熱，并使(shi)(shi)撤(che)熱控制簡(jian)(jian)單化(hua)(hua)，可以提高(gao)(gao)單位反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)的(de)(de)(de)聚(ju)(ju)合(he)量(liang)(liang)；能(neng)(neng)除(chu)(chu)去對產(chan)(chan)品性質(zhi)有(you)不(bu)良影響的(de)(de)(de)低分子量(liang)(liang)無規(gui)聚(ju)(ju)合(he)物和催(cui)化(hua)(hua)劑(ji)殘渣，可以得(de)到高(gao)(gao)質(zhi)量(liang)(liang)的(de)(de)(de)產(chan)(chan)品等優點(dian)。不(bu)足之(zhi)處是(shi)反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)氣體需要氣化(hua)(hua)，冷(leng)凝后(hou)才(cai)能(neng)(neng)循(xun)環回反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)。反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)內的(de)(de)(de)高(gao)(gao)壓液態烴類物料容量(liang)(liang)大(da)，有(you)潛在(zai)的(de)(de)(de)危險性。此(ci)外，反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)中(zhong)乙烯(xi)的(de)(de)(de)濃度不(bu)能(neng)(neng)太高(gao)(gao)，否則(ze)在(zai)反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)中(zhong)形成(cheng)一(yi)個(ge)單獨(du)的(de)(de)(de)氣相(xiang)，使(shi)(shi)得(de)反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)難以操作(zuo)，因(yin)而所得(de)共(gong)聚(ju)(ju)產(chan)(chan)品中(zhong)的(de)(de)(de)乙烯(xi)含量(liang)(liang)不(bu)會太高(gao)(gao)。

  本體(ti)法不同工藝路(lu)線的(de)區別主要(yao)是反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)的(de)不同。反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)可分為釜(fu)式反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)和環(huan)管反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)兩大(da)類(lei)。釜(fu)式反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)是利用(yong)液(ye)(ye)體(ti)蒸發的(de)潛熱(re)(re)(re)來(lai)除(chu)去反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)熱(re)(re)(re)，蒸發的(de)大(da)部(bu)分氣體(ti)經循環(huan)冷凝后返回(hui)(hui)到反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)，未(wei)冷凝的(de)氣體(ti)經壓縮機(ji)升壓后循環(huan)回(hui)(hui)反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)。而環(huan)管反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)則是利用(yong)軸(zhou)流泵使漿液(ye)(ye)高速循環(huan)，通過夾套冷卻撤熱(re)(re)(re)，由于(yu)傳熱(re)(re)(re)面積大(da)，撤熱(re)(re)(re)效果好，因此其(qi)單位反(fan)(fan)(fan)應(ying)(ying)(ying)(ying)器(qi)(qi)體(ti)積產率高，能(neng)耗低。

  本(ben)體法生產工(gong)藝(yi)按聚合(he)工(gong)藝(yi)流程，可以分(fen)為間歇式聚合(he)工(gong)藝(yi)和(he)連續式聚合(he)工(gong)藝(yi)兩種。

  a. 間歇式本體(ti)法(fa)工藝

    間(jian)歇本體法聚丙烯聚合技術是我(wo)國(guo)(guo)(guo)自行研(yan)制(zhi)開發(fa)成(cheng)功的(de)生(sheng)產(chan)(chan)(chan)(chan)技術。它具有生(sheng)產(chan)(chan)(chan)(chan)工藝(yi)技術可靠(kao)，對原料(liao)丙烯質量要(yao)求不(bu)是很高(gao)(gao)，所(suo)需催化劑國(guo)(guo)(guo)內有保證，流(liu)程簡單(dan)，投資省、收效快(kuai)，操作(zuo)簡單(dan)，產(chan)(chan)(chan)(chan)品(pin)牌號(hao)轉換(huan)靈(ling)活(huo)、“三廢少”，適合中(zhong)國(guo)(guo)(guo)國(guo)(guo)(guo)情等優(you)點(dian)，不(bu)足(zu)之處(chu)是生(sheng)產(chan)(chan)(chan)(chan)規模小，難以產(chan)(chan)(chan)(chan)生(sheng)規模效益；裝置手(shou)工操作(zuo)較(jiao)多(duo)，間(jian)歇生(sheng)產(chan)(chan)(chan)(chan)，自動化控(kong)制(zhi)水平低，產(chan)(chan)(chan)(chan)品(pin)質量不(bu)穩(wen)定；原料(liao)的(de)消耗定額較(jiao)高(gao)(gao)；產(chan)(chan)(chan)(chan)品(pin)的(de)品(pin)種牌號(hao)少，檔(dang)次不(bu)高(gao)(gao)，用(yong)途較(jiao)窄。目前，我(wo)國(guo)(guo)(guo)采(cai)用(yong)該法生(sheng)產(chan)(chan)(chan)(chan)的(de)聚丙烯生(sheng)產(chan)(chan)(chan)(chan)能(neng)(neng)力約(yue)占(zhan)全國(guo)(guo)(guo)總生(sheng)產(chan)(chan)(chan)(chan)能(neng)(neng)力的(de)24％。

  b. 連續式本體法工藝

    該工(gong)藝(yi)主要包括美國Rexall工(gong)藝(yi)、美國Phillips工(gong)藝(yi)以及日本Sumitimo 工(gong)藝(yi)。

2. Dow化學公(gong)司Unipol 工藝

   該工(gong)藝(yi)屬于(yu)Dow化(hua)學公司所有，Unipol聚丙烯工(gong)藝(yi)和(he)(he)其聚乙烯工(gong)藝(yi)類似。工(gong)藝(yi)過程主(zhu)要包括原料精制(zhi)、催化(hua)劑進(jin)料、聚合(he)反應、聚合(he)物脫氣(qi)和(he)(he)尾氣(qi)回(hui)收(shou)、造粒、摻混(hun)和(he)(he)包裝碼垛等工(gong)段(duan)。

   Unipol聚(ju)丙(bing)烯工(gong)藝流(liu)程，如圖5-107所(suo)示。

3. BASF公司的Novolen 工(gong)藝

   該工(gong)藝(yi)是由(you)(you) BASF公(gong)司開發成功的。1999年(nian)，該工(gong)藝(yi)擁(yong)有者(zhe) Targor 公(gong)司和ABB Lum-mus公(gong)司達成協(xie)議。由(you)(you)ABB Lummus 公(gong)司負責在(zai)全球(qiu)范圍內推廣Novolen工(gong)藝(yi)。2000年(nian)9月，被ABB公(gong)司和Equistar公(gong)司所組(zu)成的合資公(gong)司 Novolen Technology Holding（簡稱(cheng)NTH）收(shou)購(gou)。2008年(nian)，由(you)(you)CB＆-I整(zheng)體收(shou)購(gou)了 Lummus，Novolen 工(gong)藝(yi)由(you)(you)新成立的CB＆-ILummus負責全球(qiu)轉讓(rang)。

   Novolen 包括原料(liao)精(jing)制(zhi)、催(cui)化(hua)劑配制(zhi)、聚合反(fan)應、聚合物粉料(liao)的凈化(hua)、擠壓造(zao)粒等(deng)工(gong)序，如(ru)圖5-108和圖5-109所示。

4. 某國外工程聚丙烯裝置布置實(shi)例（圖(tu)5-110）