1. 聚丙烯工(gong)藝(yi)的技(ji)術發展
聚(ju)丙烯(xi)(xi)（Polypropylene，PP）是以丙烯(xi)(xi)為單體(ti)(ti)經(jing)聚(ju)合反應(ying)而(er)生(sheng)成(cheng)的聚(ju)合樹脂。已經(jing)成(cheng)為我國經(jing)濟(ji)建(jian)設中不可(ke)缺少的材料(liao)(liao)。具體(ti)(ti)應(ying)用(yong)(yong)(yong)在(zai)包裝材料(liao)(liao)、服裝用(yong)(yong)(yong)料(liao)(liao)、產業用(yong)(yong)(yong)料(liao)(liao)、過濾用(yong)(yong)(yong)料(liao)(liao)、衛生(sheng)用(yong)(yong)(yong)料(liao)(liao)和煙(yan)用(yong)(yong)(yong)絲束等。
四十多年來，聚(ju)丙(bing)烯的催化(hua)劑不(bu)斷開發，不(bu)斷改(gai)性(xing)，尤其(qi)是(shi)近二十年來，其(qi)技術一次又(you)一次飛躍式的進步，極大地簡化(hua)了聚(ju)丙(bing)烯的工藝流程，使裝置的投資和生產成本降到很低的水平。
聚丙(bing)烯常用工(gong)(gong)藝方法(fa)包括淤漿法(fa)工(gong)(gong)藝和(he)本體法(fa)工(gong)(gong)藝。
①. 淤(yu)漿(jiang)法(fa)工(gong)(gong)(gong)(gong)(gong)藝(yi)（Slurry Process）又稱(cheng)漿(jiang)液法(fa)或溶(rong)劑法(fa)工(gong)(gong)(gong)(gong)(gong)藝(yi)，是世界上(shang)最(zui)早用于(yu)生(sheng)(sheng)(sheng)(sheng)產(chan)聚丙烯(xi)的(de)(de)(de)工(gong)(gong)(gong)(gong)(gong)藝(yi)技術。從1957年(nian)第一(yi)套工(gong)(gong)(gong)(gong)(gong)業化(hua)裝置到(dao)現在一(yi)直是最(zui)主(zhu)要的(de)(de)(de)聚丙烯(xi)生(sheng)(sheng)(sheng)(sheng)產(chan)工(gong)(gong)(gong)(gong)(gong)藝(yi)。典(dian)型工(gong)(gong)(gong)(gong)(gong)藝(yi)主(zhu)要包括(kuo)意大利 Montedison 工(gong)(gong)(gong)(gong)(gong)藝(yi)、美(mei)國(guo)Hercules 工(gong)(gong)(gong)(gong)(gong)藝(yi)、日(ri)本三井東壓(ya)化(hua)學工(gong)(gong)(gong)(gong)(gong)藝(yi)、美(mei)國(guo)Amoco 工(gong)(gong)(gong)(gong)(gong)藝(yi)、日(ri)本三井油化(hua)工(gong)(gong)(gong)(gong)(gong)藝(yi)以及索維爾工(gong)(gong)(gong)(gong)(gong)藝(yi)等。這些工(gong)(gong)(gong)(gong)(gong)藝(yi)的(de)(de)(de)開發(fa)都基于(yu)當時的(de)(de)(de)第一(yi)代(dai)催(cui)化(hua)劑，采用立式攪拌釜反應器，需要脫(tuo)灰(hui)和(he)(he)脫(tuo)無規(gui)物，因(yin)采用的(de)(de)(de)溶(rong)劑不同(tong)，工(gong)(gong)(gong)(gong)(gong)藝(yi)流程和(he)(he)操作(zuo)條件有所不同(tong)。近(jin)(jin)年(nian)來，傳統的(de)(de)(de)淤(yu)漿(jiang)法(fa)工(gong)(gong)(gong)(gong)(gong)藝(yi)在生(sheng)(sheng)(sheng)(sheng)產(chan)中的(de)(de)(de)比例明顯減少，保(bao)留的(de)(de)(de)淤(yu)漿(jiang)產(chan)品主(zhu)要用于(yu)一(yi)些高(gao)價值領域(yu)，如特種BOPP薄膜(mo)、高(gao)相對(dui)分子質量(liang)吹塑膜(mo)以及高(gao)強度管材(cai)等。近(jin)(jin)年(nian)來，人們對(dui)該方法(fa)進(jin)行了改(gai)進(jin)，改(gai)進(jin)后(hou)的(de)(de)(de)淤(yu)漿(jiang)法(fa)生(sheng)(sheng)(sheng)(sheng)產(chan)工(gong)(gong)(gong)(gong)(gong)藝(yi)使(shi)用高(gao)活性的(de)(de)(de)第二代(dai)催(cui)化(hua)劑，可刪除催(cui)化(hua)劑脫(tuo)灰(hui)步驟，能減少無規(gui)聚合物的(de)(de)(de)產(chan)生(sheng)(sheng)(sheng)(sheng)，可用于(yu)生(sheng)(sheng)(sheng)(sheng)產(chan)均(jun)聚物、無規(gui)共聚物和(he)(he)抗沖共聚物產(chan)品等。目前世界淤(yu)漿(jiang)法(fa)PP的(de)(de)(de)生(sheng)(sheng)(sheng)(sheng)產(chan)能力約占全球PP總生(sheng)(sheng)(sheng)(sheng)產(chan)能力的(de)(de)(de)13％。
②. 本體法(fa)工藝(yi)的(de)(de)研究開發始于20世(shi)(shi)紀60年(nian)代(dai)，1964年(nian)美國Dart公司(si)采(cai)用(yong)釜(fu)式反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)建成(cheng)了世(shi)(shi)界上第(di)一套工業(ye)(ye)化(hua)(hua)本體法(fa)聚(ju)(ju)丙烯(xi)生產(chan)裝置。1970年(nian)以(yi)后，日本住友、Phillips、美國EI Psao等(deng)公司(si)都實現了液(ye)相本體聚(ju)(ju)丙烯(xi)工藝(yi)的(de)(de)工業(ye)(ye)化(hua)(hua)生產(chan)。與采(cai)用(yong)溶劑的(de)(de)漿液(ye)法(fa)相比，采(cai)用(yong)液(ye)相丙烯(xi)本體法(fa)進行聚(ju)(ju)合(he)具有不(bu)(bu)使(shi)用(yong)惰(duo)性(xing)溶劑，反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)系統內單體濃度(du)高(gao)(gao)，聚(ju)(ju)合(he)速率快(kuai)，催化(hua)(hua)劑活性(xing)高(gao)(gao)，聚(ju)(ju)合(he)反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)轉化(hua)(hua)率高(gao)(gao)，反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)的(de)(de)時空生產(chan)能力更(geng)大，能耗低(di)，工藝(yi)流程(cheng)簡單，設備少，生產(chan)成(cheng)本低(di)，“三(san)廢”量少；容易除去(qu)聚(ju)(ju)合(he)熱，并(bing)使(shi)撤熱控制簡單化(hua)(hua)，可以(yi)提高(gao)(gao)單位反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)的(de)(de)聚(ju)(ju)合(he)量；能除去(qu)對產(chan)品(pin)性(xing)質有不(bu)(bu)良影響的(de)(de)低(di)分(fen)子量無規聚(ju)(ju)合(he)物和催化(hua)(hua)劑殘渣，可以(yi)得(de)(de)到高(gao)(gao)質量的(de)(de)產(chan)品(pin)等(deng)優點。不(bu)(bu)足之(zhi)處(chu)是(shi)反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)氣體需要(yao)氣化(hua)(hua)，冷(leng)凝(ning)后才能循(xun)環回反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)。反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)內的(de)(de)高(gao)(gao)壓液(ye)態烴(jing)類物料(liao)容量大，有潛在的(de)(de)危(wei)險性(xing)。此外，反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)中乙(yi)烯(xi)的(de)(de)濃度(du)不(bu)(bu)能太(tai)高(gao)(gao)，否則(ze)在反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)中形成(cheng)一個(ge)單獨的(de)(de)氣相，使(shi)得(de)(de)反(fan)(fan)(fan)(fan)(fan)應(ying)(ying)(ying)器(qi)難以(yi)操作，因而所得(de)(de)共聚(ju)(ju)產(chan)品(pin)中的(de)(de)乙(yi)烯(xi)含量不(bu)(bu)會太(tai)高(gao)(gao)。
本體(ti)法不同工藝路線的(de)區別主要是(shi)反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)的(de)不同。反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)可分(fen)為釜式反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)和環管(guan)反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)兩大(da)類。釜式反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)是(shi)利(li)用液體(ti)蒸(zheng)發的(de)潛熱來除(chu)去(qu)反(fan)(fan)應(ying)(ying)熱，蒸(zheng)發的(de)大(da)部分(fen)氣體(ti)經循(xun)環冷(leng)凝后(hou)返回到(dao)反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)，未冷(leng)凝的(de)氣體(ti)經壓縮機升壓后(hou)循(xun)環回反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)。而(er)環管(guan)反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)則是(shi)利(li)用軸流泵使漿(jiang)液高(gao)速(su)循(xun)環，通過夾套冷(leng)卻撤(che)熱，由(you)于傳熱面積(ji)大(da)，撤(che)熱效果(guo)好，因(yin)此其單位(wei)反(fan)(fan)應(ying)(ying)器(qi)(qi)(qi)體(ti)積(ji)產率高(gao)，能耗低。
本體(ti)法生產工(gong)藝按聚合工(gong)藝流程，可(ke)以分(fen)為間歇(xie)式(shi)聚合工(gong)藝和連續(xu)式(shi)聚合工(gong)藝兩種。
a. 間歇(xie)式本(ben)體法工(gong)藝
間歇(xie)本體法聚丙烯聚合(he)技(ji)術是我國自行研制開(kai)發成功的(de)生(sheng)(sheng)(sheng)產(chan)(chan)(chan)技(ji)術。它具有生(sheng)(sheng)(sheng)產(chan)(chan)(chan)工(gong)(gong)藝(yi)技(ji)術可靠，對(dui)原(yuan)(yuan)料丙烯質量(liang)要求不(bu)(bu)是很(hen)高，所需(xu)催化劑國內有保證，流程(cheng)簡(jian)單，投資省、收效(xiao)快，操(cao)(cao)作(zuo)簡(jian)單，產(chan)(chan)(chan)品(pin)牌號轉(zhuan)換(huan)靈活、“三(san)廢少”，適合(he)中(zhong)國國情等(deng)優(you)點(dian)，不(bu)(bu)足之處是生(sheng)(sheng)(sheng)產(chan)(chan)(chan)規(gui)模小，難以產(chan)(chan)(chan)生(sheng)(sheng)(sheng)規(gui)模效(xiao)益；裝置手工(gong)(gong)操(cao)(cao)作(zuo)較(jiao)多，間歇(xie)生(sheng)(sheng)(sheng)產(chan)(chan)(chan)，自動(dong)化控制水平低，產(chan)(chan)(chan)品(pin)質量(liang)不(bu)(bu)穩定(ding)；原(yuan)(yuan)料的(de)消耗定(ding)額較(jiao)高；產(chan)(chan)(chan)品(pin)的(de)品(pin)種牌號少，檔(dang)次不(bu)(bu)高，用(yong)途較(jiao)窄。目前，我國采用(yong)該法生(sheng)(sheng)(sheng)產(chan)(chan)(chan)的(de)聚丙烯生(sheng)(sheng)(sheng)產(chan)(chan)(chan)能力(li)約(yue)占全國總(zong)生(sheng)(sheng)(sheng)產(chan)(chan)(chan)能力(li)的(de)24％。
b. 連續式本(ben)體法(fa)工藝
該工藝主要包括美(mei)國(guo)(guo)Rexall工藝、美(mei)國(guo)(guo)Phillips工藝以及日(ri)本Sumitimo 工藝。
2. Dow化學(xue)公司Unipol 工藝
該工(gong)(gong)(gong)藝(yi)屬于Dow化(hua)學公(gong)司所有，Unipol聚丙烯工(gong)(gong)(gong)藝(yi)和(he)其聚乙烯工(gong)(gong)(gong)藝(yi)類似。工(gong)(gong)(gong)藝(yi)過(guo)程主要包括原料精(jing)制、催化(hua)劑進料、聚合反應、聚合物脫氣(qi)和(he)尾(wei)氣(qi)回收、造粒(li)、摻(chan)混和(he)包裝碼垛等工(gong)(gong)(gong)段(duan)。
Unipol聚丙烯工藝流(liu)程，如圖5-107所示。
3. BASF公司的(de)Novolen 工(gong)藝
該(gai)工(gong)藝(yi)是由(you)(you) BASF公(gong)司(si)開發成(cheng)功的。1999年，該(gai)工(gong)藝(yi)擁(yong)有者 Targor 公(gong)司(si)和(he)ABB Lum-mus公(gong)司(si)達成(cheng)協議(yi)。由(you)(you)ABB Lummus 公(gong)司(si)負責在全球范圍內(nei)推廣Novolen工(gong)藝(yi)。2000年9月，被ABB公(gong)司(si)和(he)Equistar公(gong)司(si)所組成(cheng)的合資公(gong)司(si) Novolen Technology Holding（簡稱NTH）收購。2008年，由(you)(you)CB＆-I整(zheng)體收購了 Lummus，Novolen 工(gong)藝(yi)由(you)(you)新成(cheng)立的CB＆-ILummus負責全球轉(zhuan)讓。
Novolen 包括(kuo)原(yuan)料精制、催(cui)化劑配制、聚合反應、聚合物粉料的(de)凈化、擠壓造粒等工序，如圖5-108和圖5-109所示。
4. 某國外工程聚丙烯裝置布置實例（圖5-110）
