8 12.2.羧酸的制法$ 12.2.1羧酸的工业1、烃化法O2,醋酸钴CH,CH,CH,CHCH,COOH+HCOOH+CH,CH,COOH+CO+CO,+脂和酮90-100°C2-3%1-2%22%57%17%COOHCH3钻盐和锰盐3/20H20++165°C,0.88MPa,92%
§12.2. 羧酸的制法 • §12.2.1 羧酸的工业 CH3CH2CH2CH3 O2 , 90-100°C 醋酸钴 CH3COOH+HCOOH+CH3CH2COOH+CO+CO2+脂和酮 1、烃化法 57% 1-2% 2-3% 17% 22% + 3/2O2 COOH + H2O CH3 钴盐和锰盐 165°C,0.88MPa,92%
2.由一氧化碳、甲醇或乙醛制备210℃H,SOCO+NaOHHCOONaHCOOH0.6-1MPaMn(OAc)2,70-80C CH,COOHCH,CHO+1/20,0.2-0.4MPa,95-97%Rh-12,150-200°CH,OH+COCH,COOH0.5-1MPa.90-99%
2.由一氧化碳、甲醇或乙醛制备 CO+NaOH 210°C 0.6-1MPa HCOONa H2 SO4 HCOOH CH3 CHO+1/2O2 Mn(OAc) 2 ,70-80°C 0.2-0.4MPa,95-97% CH3 COOH CH3 OH+CO Rh-I 2 ,150-200°C 0.5-1MPa,90-99% CH3 COOH
12.2.2伯醇和醛的氧化K2Cr2O-H2SO4(CH3)3C-CH-C(CH3)3(CH3)3C-CH-C(CH3)382%COOHCH,OH12. 2. 3 睛的水解CH3CH3H,0,H,SO480-90%CNCOOH
12.2.2 伯 醇 和 醛 的 氧 化 (CH3)3C-CH-C(CH3)3 CH2OH K2Cr2O7-H2SO4 82% (C H3)3C-C H-C(C H3)3 COOH 1 2 . 2 . 3 腈 的 水 解CH3 CN H 2 O , H 2 S O 4 8 0 - 9 0 % C H 3 C O O H
12.2.4Grignard试剂与二氧化碳作用C(CH3)3H20,H+f'CH3)3C-COOHf'CH3):C-MgCI+O=C=O -O=C-0-MgCI+ 79-80%MgBrCOOHCO2,H20O,H+85%
12.2.4 Grignard 试剂与二氧化碳作用 £¨CH3)3C-MgCl+O=C=O O=C-O-MgCl + C(CH3)3 H2O,H+ 79-80% £¨CH3)3C-COOH MgBr CO2 ,H2O,H+ 85% COOH
12.2.5酚酸的合成ONaONaONaH,O.H*150-160°C+COCOOHCOONa 90%0.5MPaOKOKOKH+180-250°CCO2.02MPaH20COOKCOOH
ONa + CO2 150-160°C 0.5MPa ONa COONa H2O,H + 90% ONa COOH OK + CO2 180-250°C 2.02MPa OK COOK OK COOH H + H2O 12.2.5 酚酸的合成