chap 4 气固相催化反应本征动力学.ppt

1、1234567 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*000

2、0)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()/exp()

3、()/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*AAAAdAAAaAAdAAAaAAdAAaAAAdaAAAdaAdAAaAAdAAaApKpKkpKpkpKkpKpkrfkfpkrfgfhfgpKfhg fkkKhgpkkhkg

4、pkrhkgpkr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（推动力项）动力学项而)(1 /1 *MMLLBBAAAAAdAAaAdAa

5、AAMMLLBBAAAAdAAaAAdAVAaAdAaAApKpKpKpKppkrkkKkkkKpKpKpKpKpKkpk-kpk-rrr434141*111 iIIViIIIIIIIpKpKpKpp四组分吸附4422212)()()1()1(吸附项（推动力项）动力学项 MMLLBBAAMLBAMMLLBBAAMLMLsBABAsMLsBAsApKpKpKpKppkppkpKpKpKpKppKKkppKKkkkr45lmMbBaApLbBaAmMlLpMMLLBBAAVMMLLBBAALLLMMBBAApppKpppppKpKpKpKpKpKpKpKpKpKpppppp/1*)()()()(1

6、11 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）动力学项MMBBLLAApMLBAMMBBLLAAMLBAMMBBLLAAMMLLsBBAAsMMBBLLAAMMLLs

7、MMBBLLAABBAAsMLsBAsApKpKpKpKKppppkpKpKpKpKppkppkpKpKpKpKpKpKkpKpKkpKpKpKpKpKpKkpKpKpKpKpKpKkkkr5021)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 )(HpNHNHNNHppKpppppK535.125.111322321122211322322*2332223232322222223222322222222222222 5.0)()()()()()()

8、(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