chap 4 氣固相催化反應本征動力學

1、1234567 固體石蠟烴類混合物絡合物RuRhCoFeNiAlZnCuOHOHCHCHCHOHCHHCO22,43,2823/11/11/1111catAVAVcatASAScatASASAAmskmoldtdnSrdtdSrkgskmoldtdnmrdtdmrmskmoldtdnVrdtdVrdtdnVrdtdVr或準：以催化劑內表面積為基或以催化劑質量為基準：或以催化劑體積為基準：及均相反應定義：9101112131415161718總的活性中心數組分覆蓋的活性中心數被AA總的活性中心數未被覆蓋的活性中心數A1VA1Vi192021VAACdaaddaApRTQkkRTEEkkK*000

2、0)exp()exp(22VAACdaaddaApRTQkkRTEEkkK*0000)exp()exp(2324*1/1/ AAAAAdaAdaApKpKpkkpkk25*1/1/ AAAAAdaAdaApKpKpkkpkk26*11 1 ;1 BBAAVBBAABBBBBAAAAApKpKpKpKpKpKpKpK27*111 IIVIIIIIpKpKpK*JJpKJ寫為分對解離吸附的組28293031)()exp( )()exp( 0000AAddAAAaadaAfRTEkfpRTEkrrr32(a) )exp()exp( )exp()exp( )exp()exp()( )exp()()ex

3、p( )/exp()( )/exp()( , 10 /,/0000AAdAAaRThRTgAdAAaAdAdAAAaaAdAAaAAhkgpkRTkRTpkRTRTEfkRTpfRTEkrRTrfRTrf 令合并影響影響變化對影響影響變化對對中等覆蓋度的情況33)()( )ln()1exp()ln(exp( (c) (b)(c) )1exp()exp( (a),)1 (,/ (b) )ln(1 ,/ )exp()/( 0)exp()exp( (a) )exp()exp( *A*AAAAdAAAaAAdAAAaAAdAAaAAAdaAAAdaAdAAaAAdAAaApKpKkpKpkpKkpKp

4、krfkfpkrfgfhfgpKfhg fkkKhgpkkhkgpkrhkgpkr得代入將中得代入則再令令平衡時：34niAAAAdniAAAaAniAApKpKkpKpkrpK1*1*1*)()( )(經推導分子項同理：對多組分吸附，35 BASRssskkK363738394041*41*1111 iIIVMMLLBBAAAAAiIIIIIpKpKpKpKpKpKpKpK四組分吸附41abBpmMlLAbBaAmMlLpMMLLBBAAVMMLLBBAAAAAMMLLBBpKpppppppKpKpKpKpKpKpKpKpKpKpppppp/1* )()()()( 111 由42吸附項（推動

5、力項）動力學項而)( 1 / 1 *MMLLBBAAAAAdAAaAdAaAAMMLLBBAAAAdAAaAAdAVAaAdAaAApKpKpKpKppkrkkKkkkKpKpKpKpKpKkpk-kpk-rrr434141*111 iIIViIIIIIIIpKpKpKpp四組分吸附4422212)()( )1 ( )1 ( 吸附項（推動力項）動力學項 MMLLBBAAMLBAMMLLBBAAMLMLsBABAsMLsBAsApKpKpKpKppkppkpKpKpKpKppKKkppKKkkkr45lmMbBaApLbBaAmMlLpMMLLBBAAVMMLLBBAALLLMMBBAApppK

6、pppppKpKpKpKpKpKpKpKpKpKpppppp/1* )()()()( 111 由46吸附項（推動力項）動力學項 )( 1)( 1 *MMLLBBAALLLMMLLBBAALaLLLdLVLaLLdLaLdLLpKpKpKpKppkrpKpKpKpKpkpKkp-kk-rrr4748MMBBVMMBBMMMMMBBBBBLLAAVLLAALLLLLAAAAApKpKpKpKpKpKpKpKpKpKpKpKpKpKpKpK1111 11112149)2() 1()( )1)(1 ()/( )1)(1 ( )1)(1 ( )1)(1 ( )1)(1 ( 21吸附項吸附項（推動力項）動

7、力學項MMBBLLAApMLBAMMBBLLAAMLBAMMBBLLAAMMLLsBBAAsMMBBLLAAMMLLsMMBBLLAABBAAsMLsBAsApKpKpKpKKppppkpKpKpKpKppkppkpKpKpKpKpKpKkpKpKkpKpKpKpKpKpKkpKpKpKpKpKpKkkkr5021)2() 1()( nnAr吸附項吸附項（推動力項）動力學項51相應的吸附平衡分壓與氣相中分壓反應物jjjjjjdjjajdapjppKpKkpkrrr*)(52322*5 . 15 . 0*232223 )(HpNHNHNNHppKpppppK535 . 125 . 1113223

8、21122211322322*2332223232322222223222322222222222222 5 . 0)()( )( )( )()( )( HNHNHHNNNHHNHHNHNNpNdNpNaNHpNHNdNHpNHNNaNNNNNdNNaNNdNaNppkpppkrrppkpppkrKKkkKKkkpKpKkpKpKpkpKpKkpkrrr則，由實驗確定可得令54內循環(huán)式無梯度反應器外循環(huán)式無梯度反應器循環(huán)式無梯度反應器）率小于等溫微分反應器（轉化）率大于等溫積分反應器（轉化管式固定床反應器10%25%55AAAdxFdmr0)()/(/)(0AAAFmddxr5657)(120AAAAxxmFr58mxxFrAAAA)(12059RfooAfARfoo