丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)酯(zhi)(zhi)(zhi)(zhi)(zhi)的(de)(de)(de)(de)(de)(de)生(sheng)(sheng)产(chan)方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)有(you)(you)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)水(shui)解法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa),β-丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)(zhi)(zhi)(zhi)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)、雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)改(gai)良雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)、氰乙(yi)(yi)(yi)(yi)醇(chun)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)直接(jie)氧(yang)化(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)。 1.氰乙(yi)(yi)(yi)(yi)醇(chun)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 以(yi)(yi)氯乙(yi)(yi)(yi)(yi)醇(chun)和(he)氰化(hua)(hua)(hua)(hua)(hua)钠为(wei)(wei)(wei)原(yuan)料(liao)(liao),反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)生(sheng)(sheng)成(cheng)(cheng)氰乙(yi)(yi)(yi)(yi)醇(chun)、氰乙(yi)(yi)(yi)(yi)醇(chun)在(zai)(zai)(zai)(zai)硫(liu)(liu)酸(suan)(suan)(suan)(suan)存在(zai)(zai)(zai)(zai)下(xia)水(shui)解生(sheng)(sheng)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)。 2.丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)水(shui)解法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 由(you)于(yu)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)来源丰富,便发(fa)展(zhan)了用(yong)(yong)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)作(zuo)原(yuan)料(liao)(liao)生(sheng)(sheng)产(chan)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)酯(zhi)(zhi)(zhi)(zhi)(zhi)的(de)(de)(de)(de)(de)(de)方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)。现已工业化(hua)(hua)(hua)(hua)(hua)的(de)(de)(de)(de)(de)(de)方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)有(you)(you)Societe Ugine法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)Standard Oil Co(O-hio)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)。将(jiang)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)与(yu)硫(liu)(liu)酸(suan)(suan)(suan)(suan)一(yi)(yi)(yi)起加热(re)到90℃,使(shi)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)水(shui)解成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酰胺的(de)(de)(de)(de)(de)(de)硫(liu)(liu)酸(suan)(suan)(suan)(suan)盐,硫(liu)(liu)酸(suan)(suan)(suan)(suan)盐进(jin)(jin)一(yi)(yi)(yi)步酯(zhi)(zhi)(zhi)(zhi)(zhi)化(hua)(hua)(hua)(hua)(hua)生(sheng)(sheng)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)酯(zhi)(zhi)(zhi)(zhi)(zhi)。近年有(you)(you)专利(li)报道,以(yi)(yi)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)腈(jing)(jing)为(wei)(wei)(wei)原(yuan)料(liao)(liao),采用(yong)(yong)一(yi)(yi)(yi)步法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)生(sheng)(sheng)产(chan),酯(zhi)(zhi)(zhi)(zhi)(zhi)的(de)(de)(de)(de)(de)(de)收率可(ke)(ke)达95%。 3.β-丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)(zhi)(zhi)(zhi)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 以(yi)(yi)乙(yi)(yi)(yi)(yi)酸(suan)(suan)(suan)(suan)(或(huo)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)酮)为(wei)(wei)(wei)原(yuan)料(liao)(liao),磷酸(suan)(suan)(suan)(suan)三(san)乙(yi)(yi)(yi)(yi)酯(zhi)(zhi)(zhi)(zhi)(zhi)为(wei)(wei)(wei)催(cui)化(hua)(hua)(hua)(hua)(hua)剂(ji),在(zai)(zai)(zai)(zai)625-730℃下(xia)裂解生(sheng)(sheng)成(cheng)(cheng)乙(yi)(yi)(yi)(yi)烯(xi)(xi)(xi)(xi)(xi)(xi)酮。然后(hou)与(yu)无水(shui)甲醋在(zai)(zai)(zai)(zai)AICI3或(huo)BF3催(cui)化(hua)(hua)(hua)(hua)(hua)剂(ji)存在(zai)(zai)(zai)(zai)下(xia),在(zai)(zai)(zai)(zai)25℃进(jin)(jin)行(xing)(xing)气(qi)相(xiang)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying),生(sheng)(sheng)成(cheng)(cheng)β-丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)(zhi)(zhi)(zhi):如目的(de)(de)(de)(de)(de)(de)产(chan)物是丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan),则将(jiang)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)(zhi)(zhi)(zhi)与(yu)热(re)的(de)(de)(de)(de)(de)(de)100%磷酸(suan)(suan)(suan)(suan)接(jie)触(chu),便异(yi)构成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan);若目的(de)(de)(de)(de)(de)(de)产(chan)物是丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)酯(zhi)(zhi)(zhi)(zhi)(zhi),则粗丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)内酯(zhi)(zhi)(zhi)(zhi)(zhi)可(ke)(ke)不经提(ti)纯,直接(jie)与(yu)相(xiang)应(ying)(ying)(ying)(ying)(ying)的(de)(de)(de)(de)(de)(de)醇(chun)及(ji)(ji)硫(liu)(liu)酸(suan)(suan)(suan)(suan)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)。 4.雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)改(gai)良雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 第二次(ci)世界大战期间,Reppe在(zai)(zai)(zai)(zai)研究工作(zuo)中(zhong)发(fa)现了两(liang)种方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)使(shi)乙(yi)(yi)(yi)(yi)炔(gui)、一(yi)(yi)(yi)氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan)与(yu)水(shui)或(huo)醇(chun)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)合成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)或(huo)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酯(zhi)(zhi)(zhi)(zhi)(zhi)。即(ji)“化(hua)(hua)(hua)(hua)(hua)学计量(liang)(liang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)”和(he)“催(cui)化(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)”,后(hou)来经过发(fa)展(zhan)成(cheng)(cheng)为(wei)(wei)(wei)Rohm&Hass公司在(zai)(zai)(zai)(zai)生(sheng)(sheng)产(chan)中(zhong)采用(yong)(yong)的(de)(de)(de)(de)(de)(de)改(gai)进(jin)(jin)的(de)(de)(de)(de)(de)(de)雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)和(he)Dow-Badiche公司采用(yong)(yong)的(de)(de)(de)(de)(de)(de)高(gao)压(ya)雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)。 (1)化(hua)(hua)(hua)(hua)(hua)学计量(liang)(liang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 此(ci)方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)是使(shi)乙(yi)(yi)(yi)(yi)炔(gui)、羰(tang)基镍(nie)(nie)(提(ti)供一(yi)(yi)(yi)氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan))与(yu)水(shui)或(huo)醇(chun)在(zai)(zai)(zai)(zai)比较温和(he)条(tiao)件下(xia)(40℃,0.101MPa)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying),生(sheng)(sheng)成(cheng)(cheng)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)或(huo)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)酯(zhi)(zhi)(zhi)(zhi)(zhi): (2)催(cui)化(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 乙(yi)(yi)(yi)(yi)炔(gui)、一(yi)(yi)(yi)氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan)、醇(chun)在(zai)(zai)(zai)(zai)羰(tang)基镍(nie)(nie)催(cui)化(hua)(hua)(hua)(hua)(hua)剂(ji)存在(zai)(zai)(zai)(zai)下(xia),于(yu)150℃、1.50-3MPa下(xia)进(jin)(jin)行(xing)(xing)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)制得丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)酯(zhi)(zhi)(zhi)(zhi)(zhi): (3)改(gai)良雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 此(ci)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)是上(shang)述(shu)两(liang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)的(de)(de)(de)(de)(de)(de)结合,在(zai)(zai)(zai)(zai)化(hua)(hua)(hua)(hua)(hua)学计量(liang)(liang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)开始后(hou),通(tong)入(ru)一(yi)(yi)(yi)氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan)和(he)乙(yi)(yi)(yi)(yi)炔(gui),反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)即(ji)可(ke)(ke)连续进(jin)(jin)行(xing)(xing),反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)所(suo)需(xu)(xu)的(de)(de)(de)(de)(de)(de)一(yi)(yi)(yi)氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan)有(you)(you)80%可(ke)(ke)用(yong)(yong)气(qi)体一(yi)(yi)(yi)氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan),而羰(tang)基镍(nie)(nie)只需(xu)(xu)提(ti)供20%。 (4)高(gao)压(ya)雷(lei)佩(pei)(pei)(pei)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 此(ci)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)的(de)(de)(de)(de)(de)(de)特点是用(yong)(yong)四(si)氢呋(fu)喃(nan)为(wei)(wei)(wei)溶剂(ji),将(jiang)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)所(suo)需(xu)(xu)的(de)(de)(de)(de)(de)(de)乙(yi)(yi)(yi)(yi)炔(gui)先溶解在(zai)(zai)(zai)(zai)四(si)氢呋(fu)喃(nan)中(zhong),这样(yang)可(ke)(ke)减(jian)(jian)少(shao)高(gao)压(ya)处(chu)理乙(yi)(yi)(yi)(yi)炔(gui)的(de)(de)(de)(de)(de)(de)危险,同时(shi)不用(yong)(yong)羰(tang)基镍(nie)(nie),只需(xu)(xu)用(yong)(yong)镍(nie)(nie)盐作(zuo)催(cui)化(hua)(hua)(hua)(hua)(hua)剂(ji),在(zai)(zai)(zai)(zai)200-225℃和(he)8.11-10.13MPa下(xia)进(jin)(jin)行(xing)(xing)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)。 (5)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)直接(jie)氧(yang)化(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa) 丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)气(qi)相(xiang)空气(qi)催(cui)化(hua)(hua)(hua)(hua)(hua)氧(yang)化(hua)(hua)(hua)(hua)(hua)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)是生(sheng)(sheng)产(chan)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)及(ji)(ji)其酯(zhi)(zhi)(zhi)(zhi)(zhi)类的(de)(de)(de)(de)(de)(de)最新(xin)方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)。原(yuan)料(liao)(liao)消耗定额:丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)770kg/t、正(zheng)(zheng)(zheng)丁醇(chun)610kg/t。 5.制法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa): 于(yu)装有(you)(you)韦(wei)氏分(fen)馏柱(带蒸馏装置)、搅拌(ban)器(qi)、通(tong)气(qi)导管(guan)的(de)(de)(de)(de)(de)(de)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying)瓶中(zhong),加入(ru)正(zheng)(zheng)(zheng)丁醇(chun)371g(5.0mol),丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)甲酯(zhi)(zhi)(zhi)(zhi)(zhi) (2)861g(10.0mol),对(dui)苯二酚20g和(he)对(dui)甲苯磺(huang)酸(suan)(suan)(suan)(suan)10g,通(tong)入(ru)二氧(yang)化(hua)(hua)(hua)(hua)(hua)碳(tan)(tan)(tan)气(qi)体,搅拌(ban)下(xia)油浴加热(re)回流。首先蒸出的(de)(de)(de)(de)(de)(de)是甲醇(chun)-丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)甲酯(zhi)(zhi)(zhi)(zhi)(zhi)的(de)(de)(de)(de)(de)(de)共沸物(62～63℃),控制蒸馏头温度不超(chao)过65℃。约8～10h当(dang)甲醇(chun)的(de)(de)(de)(de)(de)(de)产(chan)生(sheng)(sheng)很缓慢时(shi),减(jian)(jian)压(ya)蒸出过量(liang)(liang)的(de)(de)(de)(de)(de)(de)丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)甲酯(zhi)(zhi)(zhi)(zhi)(zhi),而后(hou)减(jian)(jian)压(ya)收集(ji)39℃/1.33kPa的(de)(de)(de)(de)(de)(de)馏分(fen),得丙(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)(bing)烯(xi)(xi)(xi)(xi)(xi)(xi)酸(suan)(suan)(suan)(suan)正(zheng)(zheng)(zheng)丁酯(zhi)(zhi)(zhi)(zhi)(zhi)① (1)500～600g,收率78%～94%。注:①该方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)采用(yong)(yong)了酯(zhi)(zhi)(zhi)(zhi)(zhi)过量(liang)(liang)的(de)(de)(de)(de)(de)(de)方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)进(jin)(jin)行(xing)(xing)酯(zhi)(zhi)(zhi)(zhi)(zhi)交(jiao)换(huan)反(fan)(fan)应(ying)(ying)(ying)(ying)(ying),酯(zhi)(zhi)(zhi)(zhi)(zhi)回收后(hou)可(ke)(ke)循环使(shi)用(yong)(yong)。利(li)用(yong)(yong)该方(fang)法(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)(fa)可(ke)(ke)以(yi)(yi)合成(cheng)(cheng)如下(xia)各种酯(zhi)(zhi)(zhi)(zhi)(zhi)(表I-9- 1 参考(kao)书485页)。