chap-4-气固相催化反应本征动力学.ppt

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1、234567 固体石蜡烃类混合物络合物RuRhCoFeNiAlZnCuOHOHCHCHCHOHCHHCO22,43,2823/11/11/1111catAVAVcatASAScatASASAAmskmoldtdnSrdtdSrkgskmoldtdnmrdtdmrmskmoldtdnVrdtdVrdtdnVrdtdVr或准：以催化剂内表面积为基或以催化剂质量为基准：或以催化剂体积为基准：及均相反应定义：9101112131415161718总的活性中心数组分覆盖的活性中心数被AA总的活性中心数未被覆盖的活性中心数A1VA1Vi192021VAACdaaddaApRTQkkRTEEkkK*0000

2、)exp()exp(22VAACdaaddaApRTQkkRTEEkkK*0000)exp()exp(2324*1/1/ AAAAAdaAdaApKpKpkkpkk25*1/1/ AAAAAdaAdaApKpKpkkpkk26*11 1 ;1 BBAAVBBAABBBBBAAAAApKpKpKpKpKpKpKpK27*111 IIVIIIIIpKpKpK*JJpKJ写为分对解离吸附的组28293031)()exp( )()exp( 0000AAddAAAaadaAfRTEkfpRTEkrrr32(a) )exp()exp( )exp()exp( )exp()exp()( )exp()()exp

3、( )/exp()( )/exp()( , 10 /,/0000AAdAAaRThRTgAdAAaAdAdAAAaaAdAAaAAhkgpkRTkRTpkRTRTEfkRTpfRTEkrRTrfRTrf 令合并影响影响变化对影响影响变化对对中等覆盖度的情况33)()( )ln()1exp()ln(exp( (c) (b)(c) )1exp()exp( (a),)1 (,/ (b) )ln(1 ,/ )exp()/( 0)exp()exp( (a) )exp()exp( *A*AAAAdAAAaAAdAAAaAAdAAaAAAdaAAAdaAdAAaAAdAAaApKpKkpKpkpKkpKpk

4、rfkfpkrfgfhfgpKfhg fkkKhgpkkhkgpkrhkgpkr得代入将中得代入则再令令平衡时：34niAAAAdniAAAaAniAApKpKkpKpkrpK1*1*1*)()( )(经推导分子项同理：对多组分吸附，35 BASRssskkK363738394041*41*1111 iIIVMMLLBBAAAAAiIIIIIpKpKpKpKpKpKpKpK四组分吸附41abBpmMlLAbBaAmMlLpMMLLBBAAVMMLLBBAAAAAMMLLBBpKpppppppKpKpKpKpKpKpKpKpKpKpppppp/1* )()()()( 111 由42吸附项（推动力

5、项）动力学项而)( 1 / 1 *MMLLBBAAAAAdAAaAdAaAAMMLLBBAAAAdAAaAAdAVAaAdAaAApKpKpKpKppkrkkKkkkKpKpKpKpKpKkpk-kpk-rrr434141*111 iIIViIIIIIIIpKpKpKpp四组分吸附4422212)()( )1 ( )1 ( 吸附项（推动力项）动力学项 MMLLBBAAMLBAMMLLBBAAMLMLsBABAsMLsBAsApKpKpKpKppkppkpKpKpKpKppKKkppKKkkkr45lmMbBaApLbBaAmMlLpMMLLBBAAVMMLLBBAALLLMMBBAApppKp

6、ppppKpKpKpKpKpKpKpKpKpKpppppp/1* )()()()( 111 由46吸附项（推动力项）动力学项 )( 1)( 1 *MMLLBBAALLLMMLLBBAALaLLLdLVLaLLdLaLdLLpKpKpKpKppkrpKpKpKpKpkpKkp-kk-rrr4748MMBBVMMBBMMMMMBBBBBLLAAVLLAALLLLLAAAAApKpKpKpKpKpKpKpKpKpKpKpKpKpKpKpK1111 11112149)2() 1()( )1)(1 ()/( )1)(1 ( )1)(1 ( )1)(1 ( )1)(1 ( 21吸附项吸附项（推动力项）动力

7、学项MMBBLLAApMLBAMMBBLLAAMLBAMMBBLLAAMMLLsBBAAsMMBBLLAAMMLLsMMBBLLAABBAAsMLsBAsApKpKpKpKKppppkpKpKpKpKppkppkpKpKpKpKpKpKkpKpKkpKpKpKpKpKpKkpKpKpKpKpKpKkkkr5021)2() 1()( nnAr吸附项吸附项（推动力项）动力学项51相应的吸附平衡分压与气相中分压反应物jjjjjjdjjajdapjppKpKkpkrrr*)(52322*5 . 15 . 0*232223 )(HpNHNHNNHppKpppppK535 . 125 . 11132232

8、1122211322322*2332223232322222223222322222222222222 5 . 0)()( )( )( )()( )( HNHNHHNNNHHNHHNHNNpNdNpNaNHpNHNdNHpNHNNaNNNNNdNNaNNdNaNppkpppkrrppkpppkrKKkkKKkkpKpKkpKpKpkpKpKkpkrrr则，由实验确定可得令54内循环式无梯度反应器外循环式无梯度反应器循环式无梯度反应器）率小于等温微分反应器（转化）率大于等温积分反应器（转化管式固定床反应器10%25%55AAAdxFdmr0)()/(/)(0AAAFmddxr5657)(120AAAAxxmFr58mxxFrAAAA)(12059RfooAfARfooAfAocfofcococooiicofcooVCCVrrVCCVrrCSTRVVCCCVVVCVVVCCVVCVCV)( )( 25/ 1 )( 应速率以催化剂质量表示的反的反应速率此时以催化剂体积表示，时，反应器操作为当其中60 616263 6465结束结束