High throughput development method for catalytic hydroprocessing of dirty feedstocks

Abstract

A method for determining a set of operating parameters for a commercial scale plug flow catalytic process and reactor system for hydroprocessing dirty feedstocks, comprises the steps of: feeding selected partial pressures of said feedstock and hydrogen to the inlet the first reactor stage of a first composite multi-stage series-connected laboratory scale plug flow reactor including at least three reactor stages, the catalyst beds of each of said reactor stages including catalyst particles capable of catalyzing the removal by hydrogen of heteroatoms from said heterocyclic molecules; sampling the effluents of each of said reactor stages; measuring the concentration of heterocyclic molecules in said dirty feedstock in the concentrations of heterocyclic molecules and intermediate and final products and by products of the catalytic reaction in the effluents of each of said reactor stages.

1 . A method for determining a set of operating parameters for a commercial scale plug flow catalytic process and reactor system for hydroprocessing dirty feedstocks, comprising the steps of:
 removing heteroatoms from heterocyclic molecules in said dirty feedstock by feeding selected partial pressures of said feedstock and hydrogen to the inlet the first reactor stage of a first composite multi-stage series-connected laboratory scale plug flow reactor including at least three reactor stages, the catalyst beds of each of said reactor stages including catalyst particles capable of catalyzing the removal by hydrogen of heteroatoms from said heterocyclic molecules, said heteroatom removal process being implemented at a selected set of operating conditions of temperature, pressure, and reactant and reaction product flow rates, and the catalysts in the catalyst beds of said laboratory scale reactor stages having selected sets of characteristics;   sampling the effluents of each of said reactor stages;   measuring the concentration of heterocyclic molecules in said dirty feedstock in the concentrations of heterocyclic molecules and intermediate and final products and by products of the catalytic reaction in the effluents of each of said reactor stages;   repeating steps (a) through (c) at different selected sets of said operating conditions, and/or at different selected sets of characteristics of the catalysts in the catalyst beds of said laboratory scale reactor stages; and   using the results of said measurements obtained in one heteroatom removal operation to influence the selection of catalyst bed characteristics and operating parameters in a subsequent heteroatom removal operation for improving the productivity and selectivity of the laboratory scale plug-flow reactor.   
     
     
         2 . The method of  claim 1  wherein said measuring step includes the step of measuring the amounts of thiols, amines and alcohols in the effluents of each of said reactor stages. 
     
     
         3 . The method of  claim 1  further including the steps of:
 saturating polynuclear aromatic molecules in the effluent of the said first laboratory scale reactor by feeding selected partial pressures of effluent from the last stage of said first multistage laboratory scale reactor and hydrogen to the inlet of the first reactor stage of a second multistage series-connected laboratory scale plug flow reactor in which each of the reactor stages of said second reactor includes a catalyst bed containing catalyst particles capable of catalyzing the saturation by hydrogen of such polynuclear aromatic molecules, said polynuclear aromatic molecule saturation process being implemented at a selected set of operating conditions of temperature, pressure, and reactant and reaction product flow rates, and the catalysts in the catalyst beds of the stages of said second laboratory scale reactor having selected sets of characteristics; 
 sampling the effluents of each of the reactor stages of said second multistage series-connected reactor; 
 measuring the concentration of products and byproducts of the catalytic reactions taking place in said second multistage series-connected reactor in the effluents of each of said reactor stages of said second multistage series connected reactor; 
 repeating steps (f) through (h) at different selected sets of said operating conditions, and/or at different selected sets of characteristics of the catalysts in the catalyst beds of said second laboratory scale reactor; and 
 using the results of said measurements obtained in one polynuclear aromatic molecule saturation operation to influence the selection of catalyst bed characteristics and operating parameters in a subsequent polynuclear aromatic molecule saturation operation for improving the productivity and selectivity of said second laboratory scale plug-flow reactor. 
 
     
     
         4 . The method of  claim 3  further including the steps of:
 cleaving carbon-carbon bonds in cyclic molecules in the effluent of the said second laboratory scale reactor by feeding selected partial pressures of effluent from the last stage of said second multistage reactor and hydrogen to the inlet of the first reactor stage of a third multistage series-connected laboratory scale plug flow reactor in which each of the reactor stages includes a catalyst bed containing catalyst particles capable of catalyzing the cleaving by hydrogen of carbon-carbon bonds in cyclic molecules, said carbon-carbon bond cleaving process being implemented at a selected set of operating conditions of temperature, pressure, and reactant and reaction product flow rates, and the catalysts in the catalyst beds of the stages of said third laboratory scale reactor having selected sets of characteristics; 
 sampling the effluents of each of the reactor stages of said third multistage series-connected reactor; 
 measuring the concentration of products and byproducts of the catalytic reactions taking place in said third multistage series-connected reactor in the effluents of each of said reactor stages of said third multistage series connected reactor 
 repeating steps (k) through (m) at different selected sets of said operating conditions, and/or at different selected sets of characteristics of the catalysts in the catalyst beds of the stages of said third laboratory scale reactor; and 
 using the results of said measurements obtained in one carbon-carbon bond cleaving operation to influence the selection of catalyst bed characteristics and operating parameters in a subsequent carbon-carbon bond cleaving operation for improving the productivity and selectivity of the third laboratory scale plug-flow reactor. 
 
     
     
         5 . The method of  claim 4  further including the steps of:
 saturating unsaturated molecules in the effluent of said third multistage laboratory scale reactor by feeding selected partial pressures of effluent from the last stage of said third laboratory scale reactor and hydrogen to the inlet of the first reactor stage of a fourth multistage series-connected laboratory scale plug flow reactor in which each of the reactor stages includes a catalyst bed containing catalyst particles capable of catalyzing the saturation by hydrogen of unsaturated molecules, said unsaturated molecule saturating process being implemented at a selected set of operating conditions of temperature, pressure, and reactant and reaction product flow rates, and the catalysts in the catalyst beds of the stages of said fourth laboratory scale reactor having selected sets of characteristics; 
 sampling the effluents of each of the reactor stages of said fourth multistage series-connected reactor; and 
 measuring the concentration of products and byproducts of the catalytic reactions taking place in said fourth multistage series-connected reactor in the effluents of each of said reactor stages of said fourth multistage series connected reactor 
 repeating steps (p) through (r) at different selected sets of said operating conditions, and/or at different selected sets of characteristics of the catalysts in the catalyst beds of the stages of said fourth laboratory scale reactor; and 
 using the results of said measurements obtained in one unsaturated molecule saturating operation to influence the selection of catalyst bed characteristics and operating parameters in a subsequent unsaturated molecule saturating operation for improving the productivity and selectivity of the fourth laboratory scale plug-flow reactor. 
 
     
     
         6 . The method of  claim 4  further including the steps of:
 hydrocracking and isomerizing hydrocarbon molecules in the effluent of said third reactor by feeding selected partial pressures of effluent from the last stage of said third series-connected reactor and hydrogen to the inlet of the first reactor stage of a fourth multistage series-connected laboratory scale plug flow reactor in which each of the reactor stages includes a catalyst bed containing catalyst particles capable of catalyzing the hydrocracking and isomerization by hydrogen of hydrocarbon molecules, said hydrocracking and isomerization process being implemented at a selected set of operating conditions of temperature, pressure, and reactant and reaction product flow rates, and the catalysts in the catalyst beds of the stages of said fourth laboratory scale reactor having selected sets of characteristics; 
 sampling the effluents of each of the reactor stages of said fourth multistage series-connected reactor; 
 measuring the concentration of products and byproducts of the catalytic reactions taking place in said fourth multistage series-connected reactor in the effluents of each of said reactor stages of said fourth multistage series connected reactor; 
 repeating steps (u) through (w) at different selected sets of said operating conditions, and/or at different selected sets of characteristics of the catalysts in the catalyst beds of the stages of said fourth laboratory scale reactor; and 
 using the results of said measurements obtained in one hydrocracking and isomerization operation to influence the selection of catalyst bed characteristics and operating parameters in a subsequent hydrocracking and isomerization operation for improving the productivity and selectivity of the fourth laboratory scale plug-flow reactor. 
 
     
     
         7 . The method of  claim 5  further including the steps of:
 hydrocracking and isomerizing hydrocarbon molecules in the effluent of said fourth reactor by feeding selected partial pressures of effluent from the last stage of said fourth multistage reactor and hydrogen to the inlet of the first reactor stage of a fifth multistage series-connected laboratory scale plug flow reactor in which each of the reactor stages includes a catalyst bed containing catalyst particles capable of catalyzing the hydrocracking and isomerization by hydrogen of hydrocarbon molecules, said hydrocracking and isomerization process being implemented at a selected set of operating conditions of temperature, pressure, and reactant and reaction product flow rates, and the catalysts in the catalyst beds of the stages of said fifth laboratory scale reactor having selected sets of characteristics; 
 sampling the effluents of each of the reactor stages of said fifth multistage series-connected reactor; 
 measuring the concentration of products and byproducts of the catalytic reactions taking place in said fifth multistage series-connected reactor in the effluents of each of said reactor stages of said fifth multistage series connected reactor; 
 repeating steps (z) through (bb) at different selected sets of said operating conditions, and/or at different selected sets of characteristics of the catalysts in the catalyst beds of the stages of said fifth laboratory scale reactor; and 
 using the results of said measurements obtained in one hydrocracking and isomerization operation to influence the selection of catalyst bed characteristics and operating parameters in a subsequent hydrocracking and isomerization operation for improving the productivity and selectivity of the fifth laboratory scale reactor.