CO气相偶联合成草酸二乙酯反应热力学分析_李扬.pdfVIP

39 4 2011 4 CHEM ICAL ENG INEER ING ( CH INA ) V o .l 39 N o. 4 A pr. 2011 CO 李 扬, 胡玉容, 王 科 ( , 610225) : Joback , :; : O 642. 4 ;; :A , , CO ,, ; : 1005 9954( 2011) 04 0065 04 Therm odynam ic analysis of process for CO coupling to diethyl oxalate LI Yang, HU Y u rong, W ANG K e ( State Key L aboratory of Industrial Vent Gas Reuse, National C1 Chem ica l Engineering and T echno logy Research Center, The Southwest Research and Design Institute o f Chem ical Industry, Chengdu 610225, Sichuan P rov ince, China) A bstract: The relationsh ip betw een m o lar constant heat capacity and tem perature o f ethyl nitrite w as induced by Joback group contribution m ethod, and the standard m o lar form ation G ibbs free energy of ethy l n itrite and d iethyl carbonate w as a lso estmi ated by th is m ethod respectively. R eaction enthalpy change, reaction G ibbs free energy change and equilibrium constant o f relevant react ions occurred in the process fo r CO coup ling to d iethy l oxalate w ere calculated and analyzed together w ith basic chem ical therm odynam ic data obta ined from chem istry and eng ineer handbooks. The result show s that the low er temperature is advantageous to the form ation o f diethy l oxalate, and the reaction degree of the m a in reaction ism uch higher than that of the side react ion. K ey words: diethy l oxalate; ethy l n itrite; diethy l carbonate; coupling react ion; therm odynam ic analysis , [ 1 2] 20 80 CO [3], , ,, CO ,[ 4 7] , CO , 1 1. 1 CO : ( DEO ) ( DEC ) , ( 1982 ), , , [ 4] , [ ( 1) ] DEC [ ( 2) ] 2CO + 2C2H 5 ONO CO + 2C2H5 ONO 1. 2 ( COOC2H5 ) 2 + 2NO ( 1) CO ( C2 H5 O ) 2 + 2NO ( 2) Hf m , Sm , fGm Cp, m [ 8 14] , ( 3) ( 5) Job ack , Cp, m, 1[ 8] fG m Hf m Cp, m = nj a - 37. 93 + nj b + 0. 210 T + jj nj c - 3. 91 10- 4 T 2 + j nj d + 2. 06 10- 7 T 3 j ( 3) , : ( 028 ) E m ai:l boyliyang@ sin a. com 66 2011 39 4 fGm = 53. 88 + nj gj j ( 4) fH m = 68. 29 + nj hj j ( 5) : nj j ; a, b, c, d Job ack Cp, m , J/( m ol K ), J/( m