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Chemical Reaction Kinetics in Practice
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Edgar MurilloCopyright:
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FEATURE
#HEMICAL REACTION KINETICS
IN PRACTICE
4HE CHEMICAL REACTIONS TAKING PLACE IN THE CHEMICAL REACTOR FORM THE HEART OF ANY
CHEMICAL PROCESS 2EACTION KINETICS ARE THE TRANSLATION OF OUR UNDERSTANDING OF
THE CHEMICAL PROCESSES INTO A MATHEMATICAL RATE EXPRESSION THAT CAN BE USED IN
REACTOR DESIGN AND RATING "ECAUSE OF THE IMPORTANCE OF CORRECT AND SAFE DESIGN
OF CHEMICAL REACTORS CHEMICAL REACTION KINETICS IS A KEY ASPECT OF RESEARCH AND
DEVELOPMENT IN CHEMICAL INDUSTRIES IN RESEARCH INSTITUTES AND ACADEMIC CENTERS
AS WELL AS IN INDUSTRIAL LABORATORIES 4HERE IS AND THERE WILL ALWAYS BE A STRONG
NEED FOR KNOWLEDGE AND A SKILL BASE CONCERNING THE DETERMINATION OF REACTION
KINETICS AND THEIR APPLICATION IN THE FORM OF A KINETIC MODEL
4HIS PAPER IS A RESULT OF COOPERATION WITHIN %UROKIN A CONSORTIUM OF OVER
%UROPEAN COMPANIES AND UNIVERSITIES !N INDUSTRIAL QUESTIONNAIRE IN
HIGHLIGHTED THAT INDUSTRY IS NOT ONLY A LITTLE CONSERVATIVE IN THE METHODS IT USES
TO DETERMINE KINETICS BUT ALSO THAT THERE WAS A WIDE AWARENESS OF THE SCOPE FOR
IMPROVEMENT %UROKIN WAS THUS FOUNDED IN TO TRY AND ESTABLISH THE BEST
PRACTICES AND TO FACILITATE DEVELOPMENT WORK IN KINETICS AND ASSOCIATED AREAS
4HE PAPER BRIEmY EXPLAINS SOME UNDERLYING THEORY OF HETEROGENEOUSLY CATALYZED
CHEMICAL REACTIONS AND THEIR KINETICS )T DEALS SPECIlCALLY WITH THE ACQUISITION OF
KINETIC DATA AND GIVES RECOMMENDATIONS FOR THE SELECTION OF THE EXPERIMENTAL
REACTOR AND CONDITIONS ! PRIMARY AIM OF THIS PAPER IS DISCUSS KINETIC EXPERIMEN
TATION AND MODELING THROUGH A SERIES OF CASE STUDIES ATTEMPTING TO ILLUSTRATE
GOOD PRACTICE METHODS IN KINETIC MODELING PITFALLS AND RECOMMENDATIONS 4HE
PAPER CLOSES WITH SOME RECOMMENDATIONS AND A PERSPECTIVE ON THE FUTURE NEEDS OF
INDUSTRIAL REACTION KINETICS
2OB * "ERGER % (UGH 3TITT
'UY " -ARIN &REEK +APTEIJN *ACOB ! -OULIJN
CORRESPONDING AUTHOR
3YNETIX
0/ "OX "ILLINGHAM
#LEVELAND 43 ," 53!
4EL
&AX
E
MAIL HUGH?STITT ICICOM
6OLUME NO
RATE t F4 CONCENTRATION N
WHERE N IS TERMED THE ORDER OF REACTION
7ITH HETEROGENEOUS CATALYTIC REACTIONS THERE IS MORE THAN
ONE RATE PROCESS OCCURRING IN SERIES 4HE REACTION PROCESS
CAN BE BROKEN DOWN INTO A NUMBER OF IDENTIlABLE STEPS ALL
WITH THEIR OWN RELEVANT RATE EQUATION SOME OF WHICH MAY BE
COMBINED INTO AN OVERALL REACTION RATE EQUATION 4HE STEPS
TYPICALLY CITED ARE
-ASS TRANSFER OF REACTANTS TO THE CATALYST SURFACE
!DSORPTION OF REACTANTS ONTO CATALYST ACTIVE SITES
#ATALYTIC REACTION
$ESORPTION OF REACTION PRODUCTS
-ASS TRANSFER OF PRODUCTS AWAY FROM SURFACE
3TEPS AND ARE IDENTIlABLE mUID PHASE PHENOMENA
AS DISTINCT FROM THE SURFACE PROCESSES THAT CHARACTERIZE
ADSORPTION AND REACTION AND SPECIlCALLY A CATALYTIC REACTION
4HEY CAN AND INDEED SHOULD HAVE THEIR OWN RATE EQUATIONS
BUT DO NOT ALWAYS DO SO IN PRACTICE
4HE SURFACE PROCESS ITSELF ALSO TYPICALLY COMPRISES A
NUMBER OF DISCRETE STEPS !T ITS SIMPLEST THIS MAY BE
ENVISAGED AS THE SORPTIONnREACTIONnDESORPTION SEQUENCE
CITED ABOVE 4HE NEXT LEVEL OF MODEL COMPLEXITY THEREFORE
INCLUDES THESE STEPS EITHER AS SIMPLE STEPS OR AS COMPETITIVE
ADSORPTION OF TWO REACTANTS OR A REACTANT AND ANOTHER
COMPONENT SUCH AS A SOLVENT OR DILUENT 4HIS CAN BE DONE
INTERMEZZO
%UROKIN CHEMICAL REACTION KINETICS IN PRACTICE
7HAT ARE KINETICS
h+INETICSv IS SIMPLY A TECHNICAL TERM USED TO DESCRIBE
THE RATE OF A CHEMICAL PROCESS SUCH AS A CATALYTIC REACTION
AS A FUNCTION OF THE CONDITIONS 4HE MODELS AND THEIR
MATHEMATICAL MANIFESTATIONS VARY ENORMOUSLY IN THE LEVEL OF
COMPLEXITY AND THE DEGREE TO WHICH THEY REmECT THE ACTUAL
CHEMICAL AND PHYSICAL PROCESSES OCCURRING
!T THEIR SIMPLEST THEY CAN BE OF THE FORM
IMPLICITLY WITHIN A MATHEMATICAL EXPRESSION FOR THE REACTION
RATE !T THEIR MOST COMPLEX THE REACTION RATE EXPRESSION
CAN BE BASED ON THE MECHANISTIC OR ELEMENTAL STEPS OF THE
REACTION 4HIS CAN HAVE INCREASED MATHEMATICAL COMPLEXITY
BUT IS GENERALLY A BETTER PHYSICAL REPRESENTATION OF THE PROCESS
'IVEN THE ABOVE A NUMBER OF QUESTIONS ARISE 7HY ARE
KINETIC MODELS REQUIRED 7HY IS THERE SUCH DIVERSITY IN THE
FORM AND EXACTITUDE OF KINETIC AND RATE MODELS (OW ARE
THE EXPERIMENTAL DATA MEASURED !ND HOW ARE THE MODELS
DERIVED AND lTTED 4HIS PAPER WILL ATTEMPT TO ANSWER THESE
QUESTIONS IN THE CONTEXT OF AN INDUSTRIAL VIEWPOINT
! KEY ISSUE IS THAT AS KINETIC MODELS INCREASE IN COMPLEX
ITY THE EXPERIMENTAL EFFORT THE RANGE AND SCOPE OF EXPER
IMENTATION REQUIRED TO BUILD lT AND VALIDATE THE MODEL
ALSO INCREASE 4HE PERCEPTION IN INDUSTRY APPEARS TO BE THAT
THE EFFORT REQUIRED INCREASES BEYOND THE PROPORTIONAL GAIN
IN BENElT 4HEREFORE FROM THE POINT OF VIEW OF INDUSTRY
THE NEED FOR COMPLEX MODELS BASED ON THE PHYSICOCHEMICAL
EVENTS MUST EITHER BE JUSTIlED OR THE EFFORT REQUIRED TO
DERIVE THEM SIGNIlCANTLY REDUCED
4HIS PAPER WILL THEREFORE EXPLAIN AND ILLUSTRATE THE
NEED FOR AND THE METHODS USED TO OBTAIN RELIABLE
KINETIC DATA FOCUSING ON HETEROGENEOUS CATALYSIS )T WILL
DEAL WITH THE ACQUISITION OF KINETIC DATA GIVE SOME
THEORETICAL BACKGROUND ON KINETICS AND KINETIC MODELING
AND WILL PROVIDE RECOMMENDATIONS FOR THE SELECTION OF
THE EXPERIMENTAL REACTOR AND CONDITIONS ! MAJOR PART OF
THE PAPER WILL CONSIDER KINETIC MODELING THROUGH THE USE
OF A SERIES OF CASE STUDIES ATTEMPTING TO ILLUSTRATE GOOD
PRACTICE METHODS IN KINETIC MODELING AND PITFALLS AND
RECOMMENDATIONS )N VIEW OF THE LIMITED SPACE MASS TRANSFER
AND HYDRODYNAMIC ASPECTS WILL NOT BE COVERED IN THE CASE
%UROKIN INDUSTRY ACADEMIA COLLABORATION TOWARDS BETTER KINETICS
%UROKIN IS A CONSORTIUM OF %UROPEAN BASED COMPANIES TOGETHER
%UROKINS STATED AIM IS TO PRODUCE A PRECOMPETITIVE TOOLKIT FOR
WITH A NUMBER OF ACADEMIC CENTERS FOCUSED ON DEVELOPING PRACTICE
MEASURING KINETIC DATA AND MODEL DEVELOPMENT FOR HETEROGENEOUS
IN KINETIC MODELING 7EB SITE WWWEUROKINORG )T WAS ESTABLISHED
CATALYTIC SYSTEMS 4HE ACTIVITIES ARE CURRENTLY FOCUSED ON
IN AFTER THE NEED WAS REALIZED VIA A QUESTIONNAIRE EXTENSIVELY
I %XPERIMENTAL METHODS TO DETERMINE REACTION KINETICS EG
CITED IN THIS PAPER AND TWO WORKSHOPS IN TO BETTER
INVESTIGATION OF THE CAPABILITIES OF DIFFERENT TYPES OF LABORATORY
DElNE NEEDS AND COLLECTIVE DRIVERS )T CURRENTLY CONSISTS OF
REACTORS TO MEASURE THE KINETICS OF SPECIlC REACTION CLASSES
COMPANIES !KZO .OBEL $OW "ENELUX $3- 2ESEARCH )&0
II $EVELOPMENT OF MODELS FOR A SET OF SELECTED LABORATORY REACTOR
4ECHNIP "ENELUX 3HELL 2ESEARCH AND 4ECHNOLOGY #ENTRE 3TATOIL
SYSTEMS TO BE USED FOR PROCESSING EXPERIMENTAL DATA ANDOR
,INDE %NI4ECNOLOGIE 3YNETIX AND %# #HEM 4ECHNOLOGIES AND
THE DETERMINATION OF SUITABLE EXPERIMENTAL CONDITIONS EG
FOUR ACADEMIC CENTERS $ELFT 5NIVERSITY OF 4ECHNOLOGY 'HENT
TO ASSESS IF THE PROPOSED EXPERIMENTAL CONDITIONS ARE IN THE
5NIVERSITY .45 4RONDHEIM AND 5# ,OUVAIN 4HE MEMBERSHIP
KINETICALLY OR THE MASS TRANSFER CONTROLLED REGIME
BASE IS EVIDENTLY VERY BROAD FROM SEVEN DIFFERENT COUNTRIES
III -ETHODS FOR THE DETERMINATION OF KINETIC MODELS FROM
AND COMPANY ACTIVITIES IN OIL AND GAS PETROCHEMICALS BULK
EXPERIMENTAL DATA INCLUDING MODEL DISCRIMINATION PARAMETER
AND lNE CHEMICALS MANUFACTURE ENGINEERING CONTRACTING TO THE
ESTIMATION AND DESIGN OF EXPERIMENTS
OIL PETROCHEMICALS AND lNE CHEMICALS MARKETS AND A CATALYST
COMPANY
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
STUDIES 4HE PAPER WILL CLOSE WITH A FORWARD
LOOKING SECTION
CONSIDERING THE FUTURE NEEDS OF INDUSTRIAL REACTION KINETICS
7HY DO WE NEED KINETIC MODELS
4HIS PAPER IS A RESULT OF COOPERATION WITHIN %UROKIN )NTER
MEZZO A CONSORTIUM OF OVER %UROPEAN COMPANIES AND
UNIVERSITIES ESTABLISHED IN SPECIlCALLY TO FACILITATE
ACTIVE COLLABORATION IN THE lELD OF CATALYTIC REACTION KINETICS
4HIS INITIATIVE BY SO MANY LEADING COMPANIES GIVES AN
INDICATION OF THE IMPORTANCE THAT THE CHEMICAL INDUSTRY
ATTACHES TO KINETICS "UT WHY ARE KINETICS IMPORTANT
+NOWLEDGE OF THE RATE OF A CATALYTIC REACTION AND ITS
SELECTIVITY AS A FUNCTION OF THE PROCESS CONDITIONS AND REACTANT
CONCENTRATIONS IS ESSENTIAL FOR THE APPLICATION OF THE CATALYST
IN A COMMERCIAL REACTOR -ORE SPECIlCALLY THE KINETICS OF
THE REACTION ARE REQUIRED IN THE FORM OF A MATHEMATICAL RATE
EXPRESSION THAT CAN BE USED TO RELIABLY TRANSLATE LABORATORY
AND PILOT SCALE DATA INTO THE DESIGN OF A COMMERCIAL SCALE UNIT
4HAT RATE OR KINETIC EXPRESSION TELLS HOW THE REACTION RATE
VARIES WITH PROCESS CONDITIONS SUCH AS TEMPERATURE PRESSURE
AND COMPOSITION AND PREFERABLY ALSO WITH A MEASURE OF THE
VOLUMETRIC CONCENTRATION OF CATALYTIC SITES 4HE IMPORTANCE
OF A REACTIONS KINETICS IS THAT THE RATE AND SELECTIVITY OF A
REACTION DETERMINE THE SIZE OF THE CATALYTIC REACTOR FOR A
GIVEN OVERALL PRODUCTION RATE 7ITHOUT A RELIABLE MEANS TO
PREDICT THE REACTION RATE THE REACTOR DESIGN COULD BE HIGHLY
SPECULATIVE 4HERE ARE SEVERAL EFFECTS THAT CAN ARISE FROM THIS
UNCERTAINTY &IRSTLY WITHOUT RELIABLE ESTIMATES OF THE CAPITAL
COSTS NEEDED TO BUILD A PRODUCTION PLANT AND THE PROBABLE
OPERATING COSTS IT IS NOT POSSIBLE TO CARRY OUT A MEANINGFUL
EVALUATION OF THE ECONOMIC MERITS OF BUILDING THE PLANT
AND WITHOUT A PERSUASIVE ECONOMIC IMPERATIVE THE PLANT
IS UNLIKELY TO BE SANCTIONED 3ECONDLY AND PERHAPS MORE
IMPORTANTLY WITHOUT RELIABLE KINETICS IT IS NOT FULLY POSSIBLE TO
EVALUATE THE SIDE REACTIONS AND THE DYNAMIC EFFECTS THAT MAY
OCCUR IN THE REACTOR WHICH IS A CRITICAL STEP IN ASSESSING THE
OPERATIONAL SAFETY AND ENVIRONMENTAL IMPACT OF A CHEMICALS
PRODUCTION UNIT
CATALYST DEVELOPMENT
7HAT DOES INDUSTRY USE KINETICS FOR
4HE IMPORTANCE OF KNOWLEDGE AND OF HAVING A SKILL BASE
CONCERNING THE DETERMINATION OF REACTION KINETICS AND THEIR
APPLICATION IN THE FORM OF A KINETIC MODEL IS CLEAR 4HIS
BEGS THE QUESTION OF HOW GOOD INDUSTRY IS AT MEASURING
AND APPLYING CHEMICAL RATE MODELS AND WHAT PRECISELY IT
DOES WITH THEM 4HIS WAS PUT TO THE TEST IN WHEN
THE h#HEMICAL %NGINEERING IN THE !PPLICATIONS OF #ATALYSISv
7ORKING 0ARTY OF THE %UROPEAN &EDERATION OF #HEMICAL
%NGINEERING APPROVED A SURVEY OF INDUSTRIAL PRACTICE IN THE
MEASUREMENT AND EVALUATION OF KINETICS 4HE RESULTS OF THIS
SURVEY WERE PUBLISHED IN IN SUMMARY FORM ;= 4WENTY
FOUR CHEMICAL AND OIL COMPANIES ENGINEERING CONTRACTORS
AND CATALYST MANUFACTURERS RESPONDED TO THE QUESTIONNAIRE
AND THAT LEVEL OF RETURN INDICATES HOW SERIOUSLY INDUSTRY TAKES
THIS ISSUE 4HE RESULTS MAKE INTERESTING READING NOT ONLY
FROM THE VIEWPOINT OF HOW INDUSTRY TREATS ITS KINETICS BUT
ALSO THE DIVERSITY ACCORDING TO THE INDUSTRY SECTOR OF HOW
THEY USE THEM !DDITIONALLY A SURVEY OF THE GAPS AND
NEEDS FOR CATALYSIS IN %UROPEAN INDUSTRY ;= STRESSED THE
IMPORTANCE OF FURTHER DEVELOPMENTS IN KINETICS RESEARCH
#ONSIDER lRSTLY HOW COMPANIES USE THEIR KINETICS THE
PERCEIVED REASON FOR THE DETERMINATION OF KINETIC AND RATE
MODELS 4HE OVERALL RESULTS FROM THE SURVEY ARE SHOWN IN
&IGURE AND INDICATE A FAIRLY EVEN THREE WAY SPLIT BETWEEN
CATALYST DEVELOPMENT PROCESS DEVELOPMENT AND PROCESS
OPTIMIZATION 3IGNIlCANTLY THERE IS ONLY SMALL MINORITY USE
OF KINETIC DATA FOR MECHANISTIC RESEARCH BY CONTRAST A MAJOR
FORCE IN ACADEMIA
7HEN THE SAME DATA ARE PRESENTED BY THE INDUSTRY SECTOR
IN &IGURE SOME CLEAR TRENDS EMERGE 4HE CHEMICAL AND
OIL COMPANIES MAINLY USE KINETICS FOR PROCESS DEVELOPMENT
AND PROCESS OPTIMIZATION AND TO A SMALLER EXTENT FOR CATALYST
DEVELOPMENT !S MIGHT BE EXPECTED CATALYST PRODUCERS
FOCUS ON CATALYST DEVELOPMENT WHILE ENGINEERING COMPANIES
CONCENTRATE ON PROCESS DEVELOPMENT 3OME MECHANISTIC
RESEARCH IS DONE BY THE CATALYST PRODUCERS AND THE CHEMICAL
COMPANIES BUT THIS DOES NOT EXCEED OF THE UTILIZATION
OF KINETIC DATA
MECHANISTIC RESEARCH
PROCESS DEVELOPMENT
OTHER
&IGURE 5TILIZATION OF KINETIC DATA IN INDUSTRY
PROCESS OPTIMIZATION
MECHANISTIC RESEARCH
PROCESS DEVELOPMENT
CATALYST DEVELOPMENT
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
A CHEMICAL COMPANIES
4YPES OF COMMONLY USED RATE EXPRESSIONS
FOR THE REACTION !G "G m #G
0OWER LAW EXPRESSION
%!
R K EXP PN! P"M
24
,ANGMUIR
(INSHELWOOD
(OUGEN
7ATSON TYPE EXPRESSION
KR+ ! ADSP!+" ADSP"
R
+ ! ADSP! +" ADSP" +# ADSP#
OTHER
PROCESS OPTIMIZATION
4ABLE
B OIL COMPANIES
MECHANISTIC RESEARCH
CATALYST
DEVELOPMENT
PROCESS DEVELOPMENT
4YPES OF KINETIC MODELS
2ESEARCHERS IN CATALYSIS KINETICS AND REACTOR ENGINEERING ARE
GENERALLY WELL INFORMED ABOUT THE GENERAL THEORY CONCERNING
REACTION KINETICS !T THE SIMPLER LEVEL WE CAN DISTINGUISH TWO
COMMON BASIC APPROACHES TO REACTION MODELING SUMMARIZED
IN 4ABLE
0OWER LAW KINETICS
OTHER
&OR THE IRREVERSIBLE GAS PHASE REACTION ! " m # THE RATE OF
REACTION MAY BE REPRESENTED BY AN EXPRESSION OF THE FORM
PROCESS OPTIMIZATION
R K P!N P"M
C CATALYST COMPANIES
CATALYST DEVELOPMENT
MECHANISTIC
RESEARCH
OTHER
PROCESS OPTIMIZATION
PROCESS DEVELOPMENT
D ENGINEERING COMPANIES
MECHANISTIC
RESEARCH
CATALYST
DEVELOPMENT
OTHER
PROCESS DEVELOPMENT
WHERE P! AND P" ARE THE PARTIAL PRESSURES OF REACTANTS ! AND "
RESPECTIVELY AND K IS THE RATE CONSTANT 4HE EXPONENTS N AND
M ARE TERMED THE hORDERS OF REACTIONv
)T MAY SEEM NATURAL TO ASSUME A RATE EXPRESSION R K ;!= ;"=
WHERE THE ORDERS OF REACTION MATCH THE STOICHIOMETRIC
COEFlCIENTS AND THUS A SECOND ORDER REACTION FOR THIS
EXAMPLE lRST ORDER IN EACH REACTANT 4HIS IS NOT NECESSARILY
THE CASE ! REACTION MECHANISM CAN INCORPORATE A NUMBER OF
SUBREACTIONS AND THE POWER LAW APPROACH DISGUISES THIS 4HE
REAL RATE EXPRESSION WILL REmECT THE KINETICS OF THE POTENTIALLY
SLOWEST OR RATE
DETERMINING STEP 4HE REACTION ORDER SHOULD
THEREFORE ALWAYS BE DETERMINED EXPERIMENTALLY
4HE POWER LAW EXPRESSION IS COMMONLY USED BECAUSE OF
ITS SIMPLICITY AND ITS PROPERTY THAT IT FREQUENTLY lTS THE DATA
RATHER EASILY 4HE ANCIENT WONDER OF RECONCILING DATA BY
PLOTTING THEM ON LOG
LOG GRAPH PAPER HAS NOT FADED EVEN
IN THIS HIGH TECHNOLOGY AGE )N CATALYSIS THIS EXPRESSION
IS NOT HOWEVER BASED ON A SOUND PHYSICOCHEMICAL THEORY
AND THEREFORE THE RELIABILITY OF THE RESULTS AND PREDICTIONS IS
LIMITED TO THE RANGE OF CONDITIONS UNDER WHICH THE KINETIC
EXPERIMENTS WERE PERFORMED
PROCESS OPTIMIZATION
%FFECT OF EQUILIBRIUM
&IGURE 5TILIZATION OF KINETIC DATA FOR DIFFERENT CHEMICAL INDUSTRY SECTORS
4HE LATER PARTS OF THE SURVEY FOCUSED ON HOW INDUSTRY
MEASURES ITS DATA AND THE TYPES OF MODELS IT USES TO REPRESENT
THE KINETICS "EFORE CONSIDERING THESE ASPECTS IT IS TIMELY TO
CONSIDER THE BACKGROUND TO KINETIC THEORY THE MEASUREMENT
OF KINETIC DATA AND REACTION KINETIC MODELING
! GIVEN REACTION SUCH AS ! " m # CAN OFTEN OCCUR IN
BOTH DIRECTIONS VIZ ! " # 7HICH DIRECTION PREVAILS
AT A GIVEN CONDITION DEPENDS ON THE THERMODYNAMICS
%QUILIBRIUM CORRESPONDS TO THE MINIMIZATION OF 'IBBS
FREE ENERGY )F NO BARRIER EG ACTIVATION ENERGY EXISTS THEN
A SYSTEM WILL ALWAYS MOVE TOWARDS EQUILIBRIUM
4WO REACTIONS CAN BE DElNED EACH WITH ITS OWN RATE
EQUATION !SSUMING FOR THE SAKE OF SIMPLICITY A lRST ORDER
DEPENDENCY FOR EACH COMPONENT
! " m #
RATE R F K F ;!= ;"=
BACK REACTION
# m ! "
RATE RB KB ;#=
4HESE ARE NOT INDEPENDENT EXCEPT AT hVERY LOWv CONVERSIONS
WHERE EQUILIBRIUM IS NOT APPROACHED !T OTHER CONDITIONS
THE NET FORWARD REACTION RATE FOR ! " # IS GIVEN BY
R R F
RB K F ;!= ;"=
KB ;#=
4HUS EQUILIBRIUM OCCURS WHEN THE FORWARD AND REVERSE
REACTION RATES ARE EQUAL R F RB AND HENCE NO NET REACTION
OCCURS &OR THE REACTION ! " # THE EQUILIBRIUM CONSTANT
IS GIVEN BY +EQ [ ;#= ;!= ;"= ] EQ )T MAY THUS BE SHOWN
THAT +EQ KB K F 4HE NET FORWARD REACTION RATE IS THEREFORE
GIVEN BY R KF [ ;!= ;"= n ;#=+EQ ]
RELATIVE REACTION RATE CONSTANT
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
FORWARD REACTION
ACTIVATION ENERGY K*MOL
%FFECT OF TEMPERATURE
4HE VALUE OF THE EQUILIBRIUM CONSTANT IS A STRONG FUNCTION OF
TEMPERATURE &OR ENDOTHERMIC REACTIONS +EQ AND EQUILIBRIUM
CONVERSION INCREASE WITH TEMPERATURE WHILE FOR EXOTHERMIC
REACTIONS THE CONVERSE IS TRUE 4HIS STRONG DEPENDENCE ON
TEMPERATURE IS ALSO PREVALENT IN REACTION RATE CONSTANTS AND
SO THE NEXT LEVEL OF DETAIL TO BE INTRODUCED MAY BE THE
TEMPERATURE DEPENDENCE OF THE RATE OF REACTION 4HIS IS MOST
COMMONLY DONE USING AN !RRHENIUS
TYPE EXPRESSION
K ! EXP
%A 24
(ERE %A IS KNOWN AS THE h!CTIVATION %NERGYv 2EACTION
RATE CONSTANTS AND EQUILIBRIUM CONSTANTS COMMONLY SHOW
AGREEMENT WITH THIS RELATIONSHIP 4HIS RELATIONSHIP IS SHOWN
IN &IGURE WITH CURVES PLOTTED FOR DIFFERENT ACTIVATION ENER
GIES ALL BASED AROUND A SIMILAR RATE CONSTANT AT + )T
CAN BE SEEN THAT THE VALUE OF %A HAS A VERY STRONG INmUENCE
ON THE RATE DEPENDENCY ON TEMPERATURE 4HIS IS IMPORTANT IN
THE DESIGN OF CHEMICAL REACTORS
INTERMEZZO
INCREASING %!
4EMPERATURE #
&IGURE 2EACTION RATE STRONGLY DEPENDS ON TEMPERATURE
4HE ACTIVATION ENERGY IS A COMMONLY CITED PARAMETER
AND ITS VALUE OF COURSE TELLS THE REACTION ENGINEER HOW DEPEN
DENT THE REACTION RATE IS ON TEMPERATURE 6ALUES OF n
K*MOL ARE TYPICAL FOR MANY CATALYZED REACTIONS #OMBUS
TION AND MANY OTHER NONEQUILIBRIUM LIMITED REACTIONS MAY
HAVE MUCH HIGHER VALUES K*MOL FOR EXAMPLE ! RULE OF
THUMB OFTEN QUOTED IS THAT THE RATE OF A REACTION WILL DOUBLE
FOR EVERY + RISE IN THE REACTION TEMPERATURE 4HIS CORRE
SPONDS TO AN ACTIVATION ENERGY IN THE RANGE n K*MOL
AT TYPICAL REACTION TEMPERATURES 4HUS THE REACTION ENGINEER
4HROUGH OVERPARAMETERIZATION THE ABILITY OF THE MODEL TO EXTRAPOLATE BEYOND THE
! KINETIC MODEL WAS DERIVED FOR AN EFmUENT TREATMENT PROCESS
REACTORS WANTED TO INCREASE THROUGHPUT AND PROPOSED INCREASING
THE CATALYTIC DECOMPOSITION OF THE POLLUTANT 4HIS WAS BASED
THE OPERATING TEMPERATURE TO ACHIEVE THIS 4HE RESULT OBTAINED WITH
ON EXPERIMENTAL DATA WHERE THE REACTION WAS OBSERVED TO BE
THE ABOVE MODEL IS SHOWN IN &IGURE )T WAS SURPRISING THAT AT
IRREVERSIBLE AND lRST ORDER IN THE REACTANT 4HE DATA WERE ONLY
HIGHER TEMPERATURES THE CONVERSION WAS ESSENTIALLY INDEPENDENT OF
MEASURED OVER A NARROW TEMPERATURE RANGE THAT BELIEVED TO BE
TEMPERATURE AND EVENTUALLY EXPERIMENTAL DATA SHOWED THAT THIS WAS
THE PROBABLE OPERATING DOMAIN FOR THE INDUSTRIAL SCALE REACTOR 4HE
NOT TRUE 4HE PROBLEM LAY IN THE ADDITIONAL TEMPERATURE TERM IN THE
EXPRESSION FOR THE lRST ORDER RATE CONSTANT THAT WAS USED TO lT THE
KINETIC EXPRESSION
EXTENSIVE DATA SET WAS
)N THE lRST INSTANCE THIS ADDITIONAL TEMPERATURE TERM WAS SIMPLY
%
LNK !
A
#
4
4
#
#
REMOVED AND A SIMPLE !RRHENIUS TYPE RELATIONSHIP WAS lTTED
THROUGH THE DATA 4HIS MODIlED EXPRESSION WAS FAR MORE ABLE TO
PREDICT PERFORMANCE OUTSIDE THE EXPERIMENTAL TEMPERATURE RANGE
! COMPARISON OF THE PREDICTED DESIGN CATALYST VOLUMES TO ACHIEVE
(ERE IT CAN BE SEEN THAT THE !RRHENIUS TERM ; ! %A 4 = HAS BEEN
A GIVEN CONVERSION IS SHOWN IN &IGURE 4HE REVISED MODEL MORE
SUPPLEMENTED BY A SECOND TEMPERATURE TERM INTENDED TO IMPROVE
ACCURATELY PREDICTS THE EXPECTED TREND WHICH WAS ALSO OBSERVED
THE STATISTICAL lT FOR A TOTAL OF FOUR lTTING PARAMETERS FOR ESSENTIALLY
EXPERIMENTALLY
ONE VARIABLE 4HIS WORKED WELL UNTIL A PLANT OPERATING ONE OF THESE
EXPER
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
,ANGMUIRn(INSHELWOODn(OUGENn7ATSON KINETICS
)N ORDER TO OBTAIN A MORE MEANINGFUL KINETIC EXPRESSION IT IS
NECESSARY TO START INTRODUCING PHYSICAL AND CHEMICAL PROCESSES
OCCURRING AT THE CATALYST SURFACE INTO THE MATHEMATICAL
REPRESENTATION /NE OF THE SIMPLEST METHODS AND MOST POPULAR
APPROACHES TO THIS IS VIA THE ,ANGMUIRn(INSHELWOOD MODEL
AND THE ASSOCIATED ,ANGMUIRn(INSHELWOODn(OUGENn
7ATSON ,((7 TYPE KINETIC EXPRESSION
! ,ANGMUIRn(INSHELWOODn(OUGENn7ATSON TYPE EX
PRESSION IS DERIVED USING THE ASSUMPTIONS THAT THE ADSORPTION
OF ALL COMPONENTS CAN BE DESCRIBED BY THE ,ANGMUIRn
(INSHELWOOD MODEL AND THAT ONE SURFACE REACTION IS RATE
DETERMINING 4HE SHAPE OF THE RATE EXPRESSION DEPENDS ON
THE CHOICE OF THE RATE
DETERMINING STEP ! STUDY OF THE
THEORETICAL BACKGROUND CAN HELP THE RESEARCHER TO lND
THE MOST PROBABLE RATE
DETERMINING STEP AND TO OBTAIN
PROPER ESTIMATES OF THE KINETIC PARAMETERS WHICH CAN BE
USED AS INITIAL ESTIMATES FOR THE PARAMETER lTTING 4HESE
INITIAL ESTIMATES SHOULD ALSO BE USED TO CHECK AFTERWARDS
IF THE PARAMETERS FOUND BY THE lTTING ROUTINE ARE IN
PHYSICOCHEMICALLY ACCEPTABLE RANGES
4HIS MODEL THUS MAKES ASSUMPTIONS ABOUT ADSORPTION
AND DESORPTION ON THE CATALYST SURFACE !T ITS SIMPLEST THE
,ANGMUIRn(INSHELWOOD MODEL ASSUMES THAT ALL REACTANTS
ADSORB ONTO CATALYST SURFACES AND THAT REACTION OCCURS AS A
SURFACE PROCESS 4HIS YIELDS A KINETIC EXPRESSION OF THE FORM
RATE t
KINETIC FACTOR DRIVING FORCE
ADSORPTION TERM N
EXPERIMANTAL DOMAIN IS SEVERELY COMPROMISED CATALYTIC DECOMPOSITION REACTION
3PECIlCALLY BY USING A TEMPERATURE TERM IN ADDITION TO THE !RRHENIUS
%VENTUALLY A NEW MODEL WAS DERIVED BASED ON FURTHER
RELATIONSHIP THE lT WITHIN THE EXPERIMENTAL DOMAIN WAS IMPROVED
EXPERIMENTATION USING A ,ANGMUIR (INSHELWOOD APPROACH TO
(OWEVER THE MODEL WAS ENTIRELY USELESS WHEN ASKED TO PREDICT
ACCOUNT FOR THE INHIBITING EFFECT OF THE COMPETITIVE ADSORPTION
PERFORMANCE OUTSIDE THE DATA TEMPERATURE RANGE 4HE MODEL WAS
OF A SECOND NONREACTING COMPONENT PRESENT IN THE STREAM
IMPROVED IN THE lRST INSTANCE SIMPLY BY STRIPPING OUT THE REDUNDANT
AND PROVIDED WITH ONLY THE !RRHENIUS TYPE TERM TO DESCRIBE THE
STATISTICAL TERM
TEMPERATURE DEPENDENCE
DESIGN CATALYST VOLUME
LOG EXIT CONCENTRATION
D THE
CAN IMMEDIATELY START JUDGING THE SUSCEPTIBILITY OF A REAC
TION TO RUNAWAY SELECTIVITY LOSS OR EFFECTIVE EXTINCTION IF
THE TEMPERATURE GOES OUTSIDE THE IDEAL OPERATING WINDOW !
SIDE REACTION WITH FOR EXAMPLE AN ACTIVATION ENERGY OF
K*MOL TELLS THE DESIGN CHEMICAL ENGINEER THAT IF THE TEMPER
ATURE IS ALLOWED TO RISE THE SELECTIVITY WILL FALL RAPIDLY &UR
THERMORE UNLESS THAT SIDE REACTION IS CONSTRAINED THEN THIS
REPRESENTS A RUNAWAY POTENTIAL AND THAT MUST BE CONSIDERED
IN THE REACTOR AND CONTROL SYSTEM DESIGN
'IVEN THE PHYSICAL INTERPRETATIONS THAT CAN BE ATTACHED
TO THE ACTIVATION ENERGY IT CAN EASILY BE SEEN WHY THIS
APPROACH IS POPULAR )T IS STILL HOWEVER CONSTRAINED BY
THE mAWS OF THE EMPIRICAL POWER LAW APPROACH "ECAUSE
OF THE LACK OF PHYSICOCHEMICAL RELEVANCE THE ACCURACY OF
THE KINETIC EXPRESSION AND THE APPLICATION OF THE MODEL IS
RESTRICTED TO THE EXPERIMENTAL CONDITIONS UNDER WHICH IT WAS
DETERMINED
&OR EXAMPLE IT MAY BE TEMPTING TO IMPROVE A TEMPERATURE
lT BY INCREASING THE NUMBER OF TEMPERATURE TERMS IN THE
EXPRESSION 4HIS IS NOT ADVISABLE SEE )NTERMEZZO "Y
STATISTICALLY IMPROVING THE lT WITH A TERM THAT HAS NO PHYSICAL
MEANING THE APPLICATION OF THE MODEL IS TIGHTLY RESTRICTED
TO THE EXPERIMENTAL RANGE WHICH IN THIS CASE PREVENTED USE
OF THE ORIGINAL MODEL TO EVALUATE A REACTOR OPERATING AT AN
INCREASED TEMPERATURE 4HIS EMPHASIZES THE IMPORTANCE OF
NOT INCLUDING TOO MANY PARAMETERS IN A MODEL PARTICULARLY
WITH THOSE PARAMETERS THAT DO NOT HAVE ANY PHYSICAL
SIGNIlCANCE )T IS ALWAYS WORTH REMEMBERING THAT WITH
ENOUGH lTTING PARAMETERS A MODEL CAN BE FORCED TO lT ANY
DATA SET BUT JUST BECAUSE THERE IS A GOOD STATISTICAL lT DOES
NECESSARILY NOT MEAN THAT IT IS A GOOD MODEL
TEMPERATURE
&IGURE 0REDICTED EXIT CONCENTRATION USING 2ATE EXPRESSION
OLD MODEL
NEW MODEL
TEMPERATURE
&IGURE 0REDICTED CATALYST VOLUME TO ACHIEVE A GIVEN CONVERSION
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
4HE NUMERATOR IS A BASIC REACTION RATE EQUATION WHILE THE
DENOMINATOR ACCOUNTS FOR THE EFFECTS OF THE SORPTIVE STEPS
&OR EXAMPLE FOR A REACTION ! " m # NOT EQUILIBRIUM
LIMITED THE RATE OF FORMATION OF # IS GIVEN BY THE ,((7
TYPE EXPRESSION
R
+R+ ! !DSP!+" !DSP"
+ ! ADSP! +" !DSP" +# !DSP#
WHERE KR IS THE RATE CONSTANT FOR THE SURFACE REACTION AND
+ ! ADS + " ADS AND +# ADS ARE THE ADSORPTION COEFlCIENTS FOR THE
RESPECTIVE SPECIES
3TRICTLY THE ,ANGMUIRn(INSHELWOOD MODEL ASSUMES A
HOMOGENEOUS CATALYST SURFACE .ONHOMOGENEITY AND POTEN
TIAL ADSORPTION ONTO DIFFERENT ACTIVE SITES ARE EFFECTIVELY
ACCOUNTED FOR BY DIFFERENCES IN THE VALUES OF + ! ADS AND + " ADS
OR IN THE FORM OF THE ADSORPTION TERM 4HIS IS IN FACT ONE OF
THE STRENGTHS OF THE ,((7 MATHEMATICAL EXPRESSION )N THE
DATA lTTING AT ITS SIMPLEST THE PLOT IS EFFECTIVELY OF
Y VERSUS
A XP
BX Q
TO DESCRIBE MIXTURES BASED ON SINGLE COMPONENT PARAMETERS
AND THE ROBUSTNESS OF THE DERIVED MATHEMATICAL EXPRESSION
4HESE COMMENTS MAY APPEAR TO SUGGEST THAT THE MODEL
WORKS PRIMARILY BECAUSE OF ITS MATHEMATICAL FORM 4HIS IS
NOT TRUE 4HE UNDERLYING CONCEPT OF COMPETITIVE ADSORPTION
EQUILIBRIA ON A lNITE NUMBER OF ACTIVE SITES IMPINGING ON
THE REACTION KINETICS IS VERY IMPORTANT -ANY SYSTEMS EXIST
WHERE THE KINETICS ARE IN FACT STRONGLY AFFECTED BY ADSORPTION
PHENOMENA 4HE MOST OBVIOUS EFFECT IS WHERE A REACTANT IS
STRONGLY ADSORBED TO THE EXTENT THAT IT IS ALWAYS AVAILABLE IN
EXCESS ON THE CATALYST SURFACE 4HE REACTION RATE THUS BECOMES
INDEPENDENT OF ITS GAS PHASE CONCENTRATION OR ZERO ORDER !N
EXAMPLE OF THIS IS SHOWN IN )NTERMEZZO WHERE STRONGLY
ADSORBING SYSTEMS SHOWING ZERO HIGH CONCENTRATION LOW
CONVERSION OR lRST ORDER LOW CONCENTRATION HIGH CONVERSION
DEPENDENCIES ARE DISCUSSED !N IMPORTANT POINT IS HOW
THIS KINETIC BEHAVIOR INmUENCES THE SELECTION OF THE REACTOR
TYPE THAT WOULD BE IDEAL FOR CARRYING OUT THE REACTION AT A
COMMERCIAL SCALE
WHERE THE SIMPLE POWER LAW PLOT IS IMPROVED BY THE
DENOMINATOR THAT ALLOWS A DEGREE OF INDEPENDENT CURVATURE
4HE ,((7
TYPE EXPRESSIONS HAVE BEEN FOUND TO lT A
WIDE RANGE OF REACTIONS 7HILE THE ,ANGMUIRn(INSHELWOOD
KINETIC MODEL IS A GOOD ONE ITS REAL STRENGTH LIES IN ITS ABILITY
INTERMEZZO
:ERO ORDER KINETICS FOR A STRONGLY ADSORBING REACTANT TRANSFORM TO lRST ORDER
"ENZALDEHYDE WAS SELECTIVELY HYDROGENATED TO BENZYL ALCOHOL
LINEAR DECREASE IN A LARGE PART OF THE EXPERIMENT SHOWS THAT THE
IN THE LIQUID PHASE USING MOLECULAR HYDROGEN OVER A CATALYST
APPARENT REACTION ORDER FOR BENZALDEHYDE IS ZERO
CONSISTING OF WT .I ON A CORDIERITE MONOLITH COATED WITH
+INETIC MODELING
WT !L/
! SIMPLE ,ANGMUIRn(INSHELWOOD MODEL IS ABLE TO DESCRIBE THESE
BENZALDEHYDE
BENZYL ALCOHOL
TYPICAL EXPERIMENTAL RESULTS 5NDER THE ASSUMPTIONS THAT
TOLUENE
v BENZALDEHYDE AND HYDROGEN ADSORB ON DIFFERENT SITES
v THE SURFACE REACTION IS RATE DETERMINING
v NEARLY ALL ACTIVE SITES ARE OCCUPIED
4HE FOLLOWING SIMPLIlED EXPRESSION IS OBTAINED FOR THE REACTION RATE
OF BENZALDEHYDE R AND THE FORMATION RATE OF TOLUENE R
&IGURE SHOWS A TYPICAL RESULT FOR THE CONCENTRATION AS A FUNCTION
OF THE RESIDENCE TIME IN A BATCH RECYCLE REACTOR ;I= )N THE lRST PART
R A K
THE SELECTIVITY TOWARDS BENZYL ALCOHOL IS VERY HIGH 7HEN MOST
BENZALDEHYDE HAS BEEN CONVERTED THE RATE OF HYDROGENOLYSIS OF
WHERE K AND K INCORPORATE THE CATALYST CONCENTRATION AND THE
BENZYL ALCOHOL TO TOLUENE AND WATER BECOMES SUBSTANTIAL 4HE
HYDROGEN PRESSURE DEPENDENCY TERM + REPRESENTS THE RATIO OF
#BALD
#BALD +#BALC
R A K
#BALC
#BALD +#BALC
THE ADSORPTION CONSTANTS OF BENZYL ALCOHOL AND BENZALDEHYDE AND
A ACCOUNTS FOR CATALYST DEACTIVATION 4HE ADSORPTION OF TOLUENE IS
+INETIC PARAMETERS ESTIMATED
NEGLIGIBLE
K ; MOL MMONOLITH S =
4HE lTTED PARAMETER VALUES SHOWN IN 4ABLE INDICATE THAT THE
K ; MOL MMONOLITH S=
ADSORPTION OF BENZALDEHYDE IS STRONGER THAN THAT OF BENZYL ALCOHOL
+ ; =
4HIS EXPLAINS THE APPARENT REACTION ORDER OF ZERO FOR BENZALDEHYDE
AT HIGH CONCENTRATIONS !T HIGH CONVERSIONS THE TERM +#BALC IN THE
4ABLE +INETIC PARAMETERS ESTIMATED
DENOMINATOR BECOMES LARGER THAN THE TERM #BALD AND CAUSES THE
KINET
4URBULENT MASS TRANSFER FROM THE BULK mUID TO NEAR THE
)NTRINSIC APPARENT AND EXTRINSIC KINETICS
,AMINAR MASS TRANSFER IN THE mUID BOUNDARY LAYER OR MASS
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
CATALYST SURFACE n MM
!S NOTED IN THE INTRODUCTORY SECTION AN IMPORTANT PART
OF THE CATALYTIC REACTION PROCESS IS THE MASS TRANSFER OF THE
REACTANT TO THE CATALYST SITES 4HIS INVOLVES NOT ONLY THE
TRANSFER WITHIN THE BULK mUID PHASE BUT ALSO THE TRANSPORT
WITHIN THE POROUS STRUCTURE OF THE CATALYST PELLET OR PARTICLE
4HE ACTUAL TRANSPORT IN THE mUID PHASE CAN BE SLOW AND THUS
THE OBSERVED REACTION RATE IS IN FACT AFFECTED BY AND MAY
INDEED BE DOMINATED BY THE MASS TRANSFER PROCESS 4YPICAL
EXAMPLES HERE ARE CATALYTIC REACTIONS OCCURRING IN THE LIQUID
PHASE AND CATALYZED OXIDATION PROCESSES
)T MAY NOT BE SIMPLE EXPERIMENTALLY TO DECOUPLE THE
TRANSPORT AND KINETIC PROCESSES !FTER ALL DIFFUSION AND
KINETIC RATE FOR A lRST ORDER REACTION HAVE THE EXACT SAME
DEPENDENCY ON CONCENTRATION lRST ORDER $IFFUSION AND
MASS TRANSFER HOWEVER HAVE A MARKEDLY LOWER DEPENDENCY
ON TEMPERATURE AND THEREFORE MASS TRANSFER
INHIBITED RATES
ARE CHARACTERIZED BY AN ARTIlCIALLY DEPRESSED VALUE OF THE
ACTIVATION ENERGY AND THAT THE !RRHENIUS PLOT MAY YIELD A
CURVE RATHER THAN A STRAIGHT LINE
4HE MASS TRANSFER IN A REACTOR OCCURS ON SEVERAL DIFFERENT
LENGTH SCALES
TRANSFER lLM ABOUT THE CATALYST PARTICLE n MM
$IFFUSION WITHIN THE POROUS STRUCTURE OF THE CATALYST
n MM
!SPECTS AND ABOVE ARE CONVENIENTLY LUMPED USING THE
WELL KNOWN 7HITMAN lLM THEORY AS SEEN IN &IGURE WHICH
ASSUMES TOTAL MIXING ZERO CONCENTRATION GRADIENTS IN THE
BULK mUID AND A LAMINAR lLM WHOSE RESISTANCE TO MASS
TRANSFER IS CHARACTERIZED BY A MASS TRANSFER COEFlCIENT WHICH
IS ACTUALLY A CONDUCTANCE 4HIS RATE OF MASS TRANSFER IS LARGELY
DEPENDENT ON THE mUID PROPERTIES DENSITY VISCOSITY THE
mUID VELOCITY RELATIVE TO THE SOLID AND THE SIZE OF THE CHANNEL
IN WHICH THE mUID IS mOWING 4HERE ARE MANY EMPIRICAL
CORRELATIONS IN THE LITERATURE FOR MASS TRANSFER COEFlCIENTS ; =
AND MANY ARE DERIVED IN GEOMETRIES RELEVANT TO CATALYTIC
REACTORS
! FURTHER COMPLICATION CAN ARISE IN LIQUID PHASE REACTIONS
INVOLVING A GASEOUS REACTANT SUCH AS HYDROGENATION AND
OXIDATION USING MOLECULAR HYDROGEN AND OXYGEN RESPECTIVELY
#OMMERCIALLY THESE REACTIONS ARE TYPICALLY CARRIED OUT IN
SPARGED STIRRED TANKS OR TRICKLE BEDS )N THIS CASE THERE IS
THE ADDED STEP OF THE GASEOUS REACTANT TRANSFERRING INTO THE
KINETICS AT HIGH CONVERSION DUE TO ADSORPTION OF THE PRODUCT "ENZALDEHYDE HYDROGENATION
APPARENT REACTION ORDER FOR BENZALDEHYDE TO INCREASE TO ONE 4HIS
OF THE CONVERSION )N VIEW OF THE TRANSFORMATION INTO ST ORDER AND
WAS CONlRMED BY EXPERIMENTS WITH LOWER INTIAL CONCENTRATION )T IS
THE UNDESIRED CONSECUTIVE REACTION OF BENZYL ALCOHOL TO TOLUENE
CLEAR THAT FOR ESTIMATION OF THE PARAMETERS THE MAIN PART OF THE
HOWEVER A #342 IS NOT A SUITABLE REACTOR AND A PLUG mOW REACTOR
MEASUREMENT SHOULD BE CARRIED OUT AT LOW CONCENTRATION
IS TO BE PREFERRED IN THE lNAL CONVERSION STAGE AS A hlNISHING REAC
7HAT ARE THE CONSEQUENCES OF THE TRANSFORMATION OF TH INTO ST ORDER
TORv
KINETICS &OR ZERO
ORDER KINETICS THE REACTOR TYPE IS NOT CRITICAL AND A
CONTINUOUSLY STIRRED TANK REACTOR #342 IS SUITABLE FOR A LARGE PART
BENZYL ALCOHOL
BENZALDEHYDE
CONCENTRATION MOLM
ORDER
4HE ROLE OF MASS TRANSFER
TOLUENE
TIME S
&IGURE #ONCENTRATIONS AS A FUNCTION OF TIME DURING BENZALDEHYDE HYDROGENATION AT WT BENZALDEHYDE AT + AND -0A ;I=
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
SOLID SURFACE
OR INTERFACE
CONCENTRATION PROFILES
7HITMAN
ACTUAL
INTERMEZZO
7HEN SIMPLIFYING A MODEL BY
)N HYDRODESULPHURIZATION ($3 OF VACUUM GAS OIL IT IS WELL
)N GAS LIQUID
SYSTEMS A
FILM EXISTS ON
BOTH SIDES OF
THE INTERFACE
DOCUMENTED THAT REAL FEEDSTOCKS EG GASOIL FOLLOW AN APPARENT
SECOND ORDER BEHAVIOR IN THE AMOUNT OF SULPHUR CONTAINING
COMPONENTS SEE &IGURES AND (OW CAN THIS BE RATIONALIZED
)T IS QUITE STRANGE TO lND A SECOND ORDER BEHAVIOR WHILE THERE IS
NOT ANY SUGGESTION OF A BIMOLECULAR REACTION STEP BETWEEN TWO
SULPHUR CONTAINING MOLECULES -OREOVER THE SULPHUR PRODUCT IS
(3 ONLY
4HE EXPLANATION LIES IN THE COMPLEX COMPOSITION OF THE REAL
FLUID FLOW
VELOCITY PROFILE
CONCENTRATION
IN SOLID PHASE
FEEDSTOCK COVERING THIOETHERS THIOPHENE BENZOTHIOPHENE DI
BENZOTHIOPHENE AND SUBSTITUTED DIBENZOTHIOPHENES SEE &IGURES
AND 4HEY ALL HAVE DIFFERENT REACTIVITIES OVER A CATALYST IN ($3
7HITMAN
FILM THICKNESS
RESULTING IN THE COMPOSITE CONTRIBUTION OF ALL THESE MOLECULES IN THE
OVERALL KINETIC BEHAVIOUR
&IGURE 7HITMAN lLM THEORY FOR INTERFACIAL MASS TRANSFER
C
LIQUID PHASE EN ROUTE TO THE CATALYST SURFACE 4HIS OPENS
UP AN ADDITIONAL AREA OF MASS TRANSPORT IN CHEMICAL REACTORS
THAT DEPENDS CRITICALLY ON THE INTER
DISPERSION OF THE PHASES
AND THE REACTOR HYDRODYNAMICS 4HIS IS BEYOND THE SCOPE
OF THE PRESENT PAPER BUT HAS BEEN REVIEWED EXTENSIVELY
ELSEWHERE 3EE ;= FOR SOME RECOMMENDED REFERENCES
4HE MASS TRANSPORT WITHIN THE CATALYST PELLET MAY
BE HARDER TO CHARACTERIZE 4HE EFFECT IS EASILY OBSERVED
EXPERIMENTALLY BY VARYING THE SIZE OF THE CATALYST PARTICLE
4RADITIONALLY THIS HAS BEEN TREATED MATHEMATICALLY USING A
hPELLET EFFECTIVENESS v BASED ON THE 4HIELE MODULUS ;= !
TYPICAL PLOT OF PELLET EFFECTIVENESS AS A FUNCTION OF PELLET
SIZE FOR A lRST ORDER REACTION IS SHOWN IN &IGURE "ECAUSE
TECHNIQUES AND MODELS FOR CHARACTERIZING POROUS NETWORKS
AND MASS TRANSFER STILL DO NOT LEAD TO RELIABLE PREDICTIONS
THERE IS A TENDENCY TO MEASURE KINETICS USING THE SAME
CONCENTRATION
BED LENGTH
REACTOR ;II III=
GASOIL #O-O ALUMINA TRICKLE FLOW
, M
3
3 WT
EFFECTIVENESS
&IGURE %XPERIMENTAL RESULTS FOR HYDRODESULFURIZATION IN A lXED BED
$IFFUSIVITY % MSEC
2EACTION RATE CONSTANT SEC
PELLET DIAMETER MM
&IGURE 0ELLET EFFECTIVENESS IS A FUNCTION OF PELLET DIAMETER
CONVERSION
,(36 H
&IGURE &ITTING RESULTS FOR REACTION ORDER
LUMP
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
LUMPING BE CAREFUL NOT TO GO TOO FAR ND ORDER EFFECTS IN ($3
)T WAS DEMONSTRATED BY THE SUMMATION OF THREE lRST
ORDER REACTIONS
IN A PLUG
mOW REACTOR THAT THE COMPOSITE CONVERSION PROlLE AS A
3
2
FUNCTION OF SPACE TIME CAN BE DESCRIBED BY SECOND ORDER KINETICS
THIOETHERS
OVER A BROAD RANGE OF SPACE TIMES ;IV= 4HIS IS ILLUSTRATED IN &IGURE
AND 4ABLE
THIOPHENE
0ROBLEMS WILL ARISE IF THIS IS NOT RECOGNIZED AND A REACTOR FOR DEEP
3
($3 IS DIMENSIONED ON THE BASIS OF THE SECOND
ORDER KINETICS
4HIS WILL EVENTUALLY LEAD TO REQUIRED REACTOR VOLUMES THAT ARE TOO
LARGE WHILE A PROPER lRST
ORDER DESCRIPTION FOR THE MOST REFRACTORY
BENZOTHIOPHENE
COMPONENTS WOULD YIELD THE PROPER ANSWER
3
)N THIS CASE THREE LUMPS ARE SUFlCIENT TO DESCIBE THE KINETICS OF
THE MIXTURE OF REACTANTS ACCURATELY !N IMPORTANT QUESTION TO BE
ANSWERED IN COMPARABLE TYPES OF PROBLEMS IS WHICH AND HOW MANY
DIBENZOTHIOPHENE
LUMPED COMPONENTS SHOULD BE USED
3
SUBSTITUTED DIBENZOTHIOPHENE
3
&IGURE 3ULPHUR COMPOUNDS PRESENT IN VACUUM GAS OIL
3IMULATED DISTILLATION BP
&IGURE #OMPOSITION OF OIL FRACTIONS IN VACUUM GAS OIL
+INETICS OF THE SECOND
ORDER REACTION
USED AND THE lTTING RESULTS FOR THE THREE
lRST
ORDER REACTIONS
CONCENTRATION MOLM
DEL BY
# # #
ND ORDER REACTION DATA
#
#
#
SPACE TIME KG S MOL
&IGURE 3UCCESSFUL lT OF A SIMULATED SECOND
ORDER PROlLE BY MEANS OF
THE SUM OF THREE lRST
ORDER REACTIONS DIFFERING BY ABOUT A FACTOR OF SEVEN IN
SECOND
ORDER REACTION
REACTIVITY
K M MOL S
C MOLM
THREE lRST
ORDER REACTIONS
K S
C MOLM
K S
C MOLM
K S
C MOLM
4ABLE
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
INTERMEZZO
7HEN USING REACTION NETWORKS DONT IGNORE THE POSSIBILITY THAT INTERMEDIATES REACT
!S PART OF THE HYDRODENITROGENATION ($. NETWORK OF QUINOLINE
FUNCTION OF THE SPACE TIME IN THE REACTOR &IGURE 4HIS IS EXPLAINED
THE CONVERSION OF OF ORTHOPROPYLANILINE /0! INTO PROPYL BENZENE
BY THE FACT THAT DURING THE REACTION THERE WILL BE A COMPETITION
0" PROPYLCYCLOHEXENE 0#(% AND PROPYLCYCLOHEXANE 0#(
BETWEEN DESORPTION AND CONSECUTIVE REACTION OF THE SURFACE SPECIES
HAS BEEN STUDIED &IGURE SHOWS THE KINETIC SCHEME
4HAT PART OF THE ADSORBED /0! WILL REACT IN CONSECUTIVE STEPS TOWARDS
4HE REACTIONS STARTING FROM /0! SHOW lRST ORDER DEPENDENCIES
THE lNAL PRODUCT ACCOUNTS FOR THIS @DIRECT REACTION STEP )NTERMEDIATE
4HE REACTION ALSO PROCEEDS VIA THE PROPYLCYCLOHEXYLAMINE 0#(!
SPECIES DONT NECESSARILY HAVE TO DESORB lRST BEFORE REACTING FURTHER
INTERMEDIATE WHICH IS OBSERVED ONLY IN TRACES
IN A CONSECUTIVE STEP 4HIS IS AN IMPORTANT ASPECT OFTEN OVERLOOKED
)NCLUDED IN THIS SCHEME IS THE DIRECT CONVERSION OF /0! TO 0#(
IN CONSECUTIVE REACTION SCHEMES AS IN SELECTIVE HYDROGENATIONS
TO OBTAIN A GOOD DESCRIPTION OF THE PRODUCT CONCENTRATIONS AS A
AND OXIDATIONS AND DEPENDS ON THE RELATIVE MAGNITUDE OF THE
K
0"
/0!
K
K
PARTIAL PRESSURE K0A
.(
/0!
0#(
0#(%
0"
0#(%
K
0#(
&IGURE 2EACTION SCHEME OF THE ($. OF ORTHOPROPYLANILINE /0!
SPACE TIME S
&IGURE +INETICS OF THE ($. OF ORTHOPROPYL ANILINE /0! OVER .I-O AT
# ONE SITE MODEL ;V=
CATALYST PELLET SIZE AS WILL BE USED IN THE OPERATING PLANT
)N MANY CASES THIS LEADS TO A KINETIC MODEL THAT INHERENTLY
INCLUDES INTRAPARTICLE MASS TRANSPORT RATE EFFECTS
#LEARLY IT IS ESSENTIAL TO DISTINGUISH BETWEEN MODELS THAT
INCLUDE ONLY CHEMICAL EFFECTS AND THOSE THAT INCLUDE VARYING
DEGREES OF MASS TRANSFER 2EGARDING MASS TRANSFER WE CAN
DElNE THREE LEVELS OF A MODEL
A )NTRINSIC WHERE ALL THE EFFECTS OF MASS TRANSPORT HAVE
BEEN STRIPPED OUT AND THE MODEL REPRESENTS ONLY THE SUR
FACE PROCESSES
B !PPARENT WHERE ANY TRANSPORT LIMITATIONS INTERNAL TO
THE CATALYST STRUCTURE ARE INCLUDED IN THE MODEL -EASUR
ING KINETICS ON A FULL
SIZED PELLET IS AN EXAMPLE OF THIS
7HILE MAYBE NOT STRICTLY CORRECT FROM A SCIENTIlC POINT
OF VIEW IT IS NONETHELESS PRAGMATIC
C %XTRINSIC WHERE NO ATTEMPT HAS BEEN MADE TO DECOU
PLE THE GROSS MASS TRANSFER FROM THE REAL OR INTRINSIC
KINETICS 4HE MODEL MAY THEREFORE INCLUDE EFFECTS RELATED
TO GROSS MIXING TIMES AND DIFFUSION THROUGH THE LAMINAR
lLM ADJACENT TO THE CATALYST SURFACE
/NE lNAL POINT HERE IS THAT IN DEVELOPING AN INTRINSIC
MODEL IT BEHOVES THE EXPERIMENTER TO VERIFY THE ABSENCE OF
TRANSPORT EFFECT 4HERE IS MUCH GUIDANCE IN THE LITERATURE ON
HOW TO DO THIS ;= )T IS CLEAR HOWEVER THAT THIS IS NOT ALWAYS
DONE
-ODELING MORE COMPLEX SYSTEMS
-ANY REAL SYSTEMS ARE COMPLEX INVOLVING MULTIPLE
COMPONENTS OF FEASIBLE REACTIONS 7HILE IT IS POSSIBLE TO
TREAT SUCH SYSTEMS EXHAUSTIVELY IT IS RARELY PRACTICAL TO DO
SO 4ECHNIQUES HAVE THEREFORE BEEN DEVELOPED TO SIMPLIFY
SYSTEMS ON A RATIONAL BASIS SO THAT THE REACTION KINETICS CAN
BE CHARACTERIZED WITHOUT EXCESSIVE EXPERIMENTATION AND BY
USING A MATHEMATICAL MODEL OF APPROPRIATE COMPLEXITY 4WO
TECHNIQUES COMMONLY USED ARE LUMPED MODELS AND REACTION
NETWORKS
,UMPED MODELS
!S THE NAME SUGGESTS THE ESSENCE OF THIS IS SIMPLIlCATION BY
COLLECTING RELATED VARIABLES 4HIS HAS BEEN REFERRED TO ALSO AS
vLUMPED PARAMETER MODELv 4HIS HOWEVER IS A MISNOMER AS
IT IS THE CHEMICAL SPECIES RATHER THAN THE PARAMETERS THAT ARE
GROUPED 4HIS IS TYPICALLY APPLIED TO GROUPS OF CHEMICALS OF
SIMILAR PROPERTIES 4HIS IS A POWERFUL METHOD BUT SHOULD BE
DONE HOWEVER WITH EXTREME CARE AND WITH DUE ATTENTION TO
WHETHER THE SIMPLIlCATIONS ARE IN FACT VALID !S AN EXAMPLE
)NTERMEZZO SHOWS THE EXPLANATION OF THE OFTEN
OBSERVED
APPARENT SECOND ORDER BEHAVIOR BUT WHICH WAS FOUND UNABLE
TO DESCRIBE DEEP ($3 ACCURATELY 4HE CAUSE IS OVERSIMPLI
lCATION 2EDUCING THE MODEL TO ONE hLUMPv IS EXCESSIVE
WHEREAS A THREE hLUMPv MODEL CAN DESCRIBE THE DEEP ($3
FURTH
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
EACT
FURTHER WITHOUT DESORPTION AND SUBSEQUENT RE ADSORPTION (YDRODENITROGENATION OF QUINOLINE
CORRESPONDING RATE CONSTANTS INVOLVED /F COURSE IF ADSORPTION
YIELDING A lRST ORDER DEPENDENCY 3IMILAR OBSERVATIONS HAVE BEEN
DESORPTION EQUILIBRIUM IS ASSUMED THIS PHENOMENON WILL NOT OCCUR
MADE FOR THE MORE COMPLEX REACTION SCHEME IN THE SELECTIVE
4HIS TYPE OF MODEL DEVIATES THEREFORE FROM THE CLASSICAL ,((7
HYDROGENATION OF CINNAMALDEHYDE ;VI=
MODEL WITH ONE RATE DETERMINING STEP
4HE 0#( FORMATION CAN BE DESCRIBED BY lRST
ORDER IRREVERSIBLE
REACTIONS FROM /0! AND FROM 0#(% !LTHOUGH /0! WILL STRONGLY
ADSORB AT THE CATALYST AND HENCE A ZERO
ORDER IS ANTICIPATED THE
EQUALLY STRONG AMMONIA PRODUCT ADSORPTION RESULTS IN A CONSTANT
DENOMINATOR OF THE RATE EXPRESSION INDEPENDANT OF CONVERSION
COMPETITIVE PARALLEL STEPS
DIRECT GLOBAL ROUTES
KA KB K/0! P/0!
R/0! n
KA
K/0! P/0! K.( P.(
KC KD
/0!
/0!
FAST REACTION STEPS
KA
KB
0#(!
0#"
SLOW
0#(%
KD
THE DIRECT ROUTE TO 0#(
(#S NOT ADSORBED WEAKLY COMPARED TO . S
0#(!
KC
ONLY TRACES FOUND
0#(%
KE
0#(
&IGURE 0ROPOSED MECHANISM FOR THE ($. OF ORTHOPROPYL ANILINE /0! OVER .I-O ONE SITE MODEL ;V=
RESULTS ACCURATELY 4HIS EXAMPLE ILLUSTRATES ALSO THAT ONE
SHOULD AVOID DERIVING THE KINETIC MECHANISM FROM VISUAL
INSPECTION OF THE EXPERIMENTAL DATA ONLY 4HE USE OF A LIM
ITED RANGE OF EXPERIMENTAL CONDITIONS MAY RESULT IN AN OVER
ALL PICTURE DESCRIBED BY SIMPLE KINETIC EQUATIONS THAT MAY
DRAMATICALLY FAIL WHEN EXTRAPOLATED
2EACTION NETWORKS
! REACTION NETWORK IS ESSENTIALLY A MAPPING EXERCISE OF THE
FEASIBLE REACTIONS IN A SYSTEM WHERE MULTIPLE REACTIONS ARE
POSSIBLE BOTH IN SERIES AND IN PARALLEL ! TYPICAL EXAMPLE
IS SHOWN IN )NTERMEZZO 4HIS CASE STUDY HIGHLIGHTS A
POTENTIAL PROBLEM WITH THIS APPROACH BASIC ASSUMPTIONS
OF REACTION PATHS )T IS ALL TOO EASY TO ASSUME THAT ALL REACTIONS
OCCUR AS DISCRETE ADSORPTIONnREACTIONnDESORPTION CYCLES AND
NEGLECT THE FACT THAT AN INTERMEDIATE DOES NOT NECESSARILY
HAVE TO DESORB BEFORE IT REACTS FURTHER 4HIS IS IN FACT QUITE
COMMON
4HEORETICALLY
BASED KINETIC MODELS
)T IS POSSIBLE TO BUILD KINETIC MODELS FROM THEORETICAL
AND MECHANISTIC CONSIDERATIONS OF THE REACTION ! COMMON
APPROACH IS THE SO CALLED ELEMENTARY STEP APPROACH WHERE
THE REACTION MECHANISM IS DESCRIBED BY A SET OF SINGLE EVENTS
EACH OF WHICH CAN BE ASCRIBED A RATE EQUATION OR A TERM
IN A SINGLE RATE EQUATION 4HIS CLEARLY HAS THE POTENTIAL
TO LEAD TO VERY COMPLEX MODELS WITH LARGE NUMBERS OF
lTTING PARAMETERS )F THIS TECHNIQUE IS USED PROPERLY THE
MECHANISTIC UNDERSTANDING CAN IN FACT LEAD TO SIMPLE MODELS
AND EQUATIONS THROUGH THE RATIONAL ELIMINATION OF SOME OF
THE STEPS IN ORDER TO FOCUS ON THE RATE LIMITING STEPS AND KEY
COMPETITIVE PROCESSES IN THE CASE OF PARALLEL REACTIONS
4HE DESCRIPTION OF THE REACTION KINETICS OF COMPLEX
REACTION NETWORKS REQUIRES A MODELING APPROACH MORE
SOPHISTICATED THAN SIMPLY ADJUSTING THE KINETIC PARAMETERS FOR
EACH REACTION INDEPENDENTLY ! WELL ESTABLISHED APPROACH FOR
DEVELOPING AND USING A FUNDAMENTAL MODEL FOR HYDROCRACKING
OF PARAFlNS IS SHOWN IN )NTERMEZZO 4HIS ALSO PROVES
THAT KINETIC MODELING BASED ON FUNDAMENTALS DOES NOT
NECESSARILY REQUIRE lTTING OF A LARGE NUMBER OF KINETIC
PARAMETERS BUT THAT ON THE CONTRARY PROPER FUNDAMENTAL
MODELS MAY REDUCE THE TOTAL NUMBER OF lT PARAMETERS
SIGNIlCANTLY WITHOUT LOSING THE RELIABILITY OF THE MODEL
IF EXTRAPOLATED !NOTHER METHOD FOR THE MATHEMATICAL
TREATMENT OF THE KINETICS IN REACTION NETWORKS CAN BE FOUND
IN 4EMKIN ;=
7HAT TYPES OF KINETIC MODELS DOES INDUSTRY USE
)N THEIR REPORT ON THE INDUSTRIAL QUESTIONNAIRE "OS ET AL ;=
CLASSIFY MODELS ACCORDING TO THE COMPLEXITY AND THE EXTENT
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
#LASSIlCATION OF KINETIC MODELS
"OS ET AL ;=
-ODEL TYPES
3IMPLE lRST ORDER OR POWER LAW
,((7 ,ANGMUIRn(INSHELWOOD n(OUGENn7ATSON
N
LUMPED MODELS FOR COMPLEX SYSTEMS
$ETAILED MECHANISTIC MODEL
!B INITIO MOLECULAR DYNAMICS
-ODEL LEVEL
! )NTRINSIC KINETIC MODELS EXCLUDING ALL TRANSPORT EFFECTS
" !PPARENT KINETIC MODELS THAT INCLUDE INTERNAL TRANSPORT EFFECTS
# %XTRINSIC MODELS INCLUDING ALL TRANSPORT EFFECTS PLUS KINETICS
OF DECOUPLING OF MASS TRANSFER )T WILL BE REPRODUCED HERE AS
IT HIGHLIGHTS THE DIFFERENT APPROACHES
#ONCERNING THE TYPE OF KINETIC EXPRESSIONS USED WITHIN
THE COMPANIES MOST OF THE RESPONDENTS STATED THAT IN
PRINCIPLE ONE SHOULD STRIVE FOR INTRINSIC KINETICS BUT
NEVERTHELESS THE MAJORITY FOR VARIOUS REASONS FREQUENTLY DO
NOT SEPARATE ALL TRANSPORT PHENOMENA FROM THE CHEMICAL
REACTION KINETICS 4HAT IS WHILE THE ADVANTAGES OF INTRINSIC
KINETICS ARE ACKNOWLEDGED THESE ADVANTAGES DO NOT ALWAYS
OUTWEIGH THE DIFlCULTIES IN OBTAINING THEM 3PECIlCALLY IF
ANY OF HYDRODYNAMICS MASS TRANSFER AND KINETICS CAN BE
LUMPED AND SCALED BY SIMILARITY THEN THIS IS OSTENSIBLY THE
SIMPLEST AND MOST FAVORED ROUTE ALBEIT ONE THAT MAY BE
FRAUGHT WITH DIFlCULTIES
+INETIC MODELS ARE MOSTLY SIMPLE lRST OR N TH ORDER OR
,ANGMUIRn(INSHELWOOD TYPE EXPRESSIONS MORE COMPLEX
KINETIC MODELS ARE SCARCELY USED 3IMPLICITY AND MINIMIZATION
4ABLE
INTERMEZZO
+INETIC MODELING BASED ON FUNDAMENTALS DOES NOT NECESSARILY REQUIRE A LARGE
4O THE CONTRARY PROPER FUNDAMENTAL MODELS MAY SIGNIlCANTLY
2EACTION CHEMISTRY
REDUCE THE TOTAL NUMBER OF lT PARAMETERS WITHOUT LOSING THE
(YDROCRACKING CATALYSTS ARE BIFUNCTIONAL IE THEY CONTAIN A
RELIABILITY OF THE MODEL IF EXTRAPOLATED 4HIS IS SHOWN HERE WITH
HYDROGENATION FUNCTION ON AN ACIDIC CARRIER 4HE METAL CATALYZED
REFERENCE TO A FUNDAMENTAL MODEL FOR HYDROCRACKING
REACTIONS AND THE ELEMENTARY ACID
CATALYZED REACTIONS CONSIDERED IN
THE HYDROCRACKING OF ALKANES ARE DEPICTED IN &IGURE 0HYSISORPTION
3COPE
OF ALKANES AND ALKENES INTO THE ZEOLITE PORES PRECEDES THESE REACTION
(YDROCRACKING OF HEAVY HYDROCARBONS REPRESENTS A CASE TYPICAL
STEPS !LKANES OR CYCLOALKANES DEHYDROGENATE ON THE METAL SITES
FOR RElNING OIL 4HE PRODUCTION CAPACITY OF RElNERY UNITS CAN BE
WITH FORMATION OF UNSATURATED CYCLO ALKENES WHICH IN TURN MIGRATE
AS HIGH AS ONE MILLION TON PER YEAR IE AMONG THE LARGEST IN
TO THE "RNSTED ACID SITES OF THE CARRIER WHERE THEY ARE PROTONATED
THE INDUSTRY (ENCE EVEN VERY MARGINAL IMPROVEMENTS IN PRODUCT
YIELDING CARBENIUM IONS 4HE LATTER UNDERGO REACTIONS SUCH AS
YIELDS HAVE SIGNIlCANT EFFECTS ON THE PROCESS ECONOMICS 4HIS
HYDRIDE AND ALKYL SHIFTS SCRAMBLING THE POSITION OF THE CHARGE OR
PROVIDES A STRONG INCENTIVE TO USE DETAILED KINETIC MODELS
OF THE ALKYL SUBSTITUENTS PROTONATED CYCLOPROPANE 0#0 BRANCHING
! KEY FEATURE OF RElNING PROCESSES IS THE COMPLEX COMPOSITION OF
ALTERING THE NUMBER OF SUBSTITUENTS AND CRACKING CLEAVING THE # #
THE FEED AND PRODUCT STREAMS 4HOUSANDS RATHER THAN HUNDREDS
BOND IN B POSITION OF THE POSITIVE CHARGE
OF MOLECULES ARE INVOLVED !T lRST SIGHT THE LUMPING OF INDIVIDUAL
MOLECULES WITH SIMILAR PHYSICAL AND CHEMICAL PROPERTIES SEEMS
2ATE EQUATIONS
VERY ATTRACTIVE 3UCH AN APPROACH IS FACED WITH SEVERAL DRAWBACKS
!CCOUNTING FOR ALL THE POSSIBLE REACTION INTERMEDIATES LEADS TO HUGE
HOWEVER THE LACK OF A CLEAR PHYSICAL MEANING OF THE KINETIC
REACTION NETWORKS 3TARTING FROM FOR EXAMPLE N NONADECANE
PARAMETERS IN THE LUMPED MODEL BEING THE MAIN ONE 4HIS REQUIRES
ALKANES ALKENES AND CARBENIUM IONS INVOLVED IN
A REGRESSION OF EXPERIMENTAL DATA TO OBTAIN ESTIMATES OF THE
DE HYDROGENATIONS DE PROTONATIONS HYDRIDE SHIFTS
VALUES OF THE LATTER !CTUALLY THESE VALUES CAN EVEN DEPEND ON
ALKYL SHIFTS 0#0 BRANCHINGS AND B SCISSIONS
THE FEEDSTOCK COMPOSITION -OREOVER THE NUMBER OF PARAMETERS
HAVE TO BE CONSIDERED IN THE lRST INSTANCE )T IS VERY REASONABLE
INCREASES DRASTICALLY WHEN MORE LUMPS HAVE TO BE CONSIDERED IN
HOWEVER TO ASSUME THAT THE THERMODYNAMIC AND KINETIC PROPERTIES
ORDER TO ENABLE THE MODEL TO CALCULATE RELEVANT PROPERTIES OF THE
OF THE INDIVIDUAL HYDROCARBON SPECIES ARE COMPLETELY DETERMINED BY
PRODUCT STREAMS SUCH AS THE OCTANE NUMBER &INALLY IT IS HARD TO
THE NATURE OF THE CARBON ATOMS DIRECTLY INVOLVED WITH THE ELEMENTARY
ACCOUNT FOR THE EFFECT OF CATALYST PROPERTIES ON THE KINETICS
REACTIONS )N THE SO CALLED SINGLE EVENT APPROACH DEVELOPED BY
.ONE OF THE ABOVE DISADVANTAGES ARE SHOWN BY THE SO CALLED
&ROMENT AND CO WORKERS ;VII= THE POSSIBLE EFFECTS OF THE SKELETAL
FUNDAMENTAL MODELS BASED ON THE KINETICS OF THE ELEMENTARY
STRUCTURE OF THE REACTING SPECIES ON THE RATE COEFlCIENTS ARE
REACTIONS OCCURRING BETWEEN THE INDIVIDUAL MOLECULES PROVIDED
NEGLECTED EXCEPT FOR THE GLOBAL SYMMETRY (ENCE THE LATTER ONLY
SOME REASONABLE ASSUMPTIONS BASED ON THE UNDERLYING CHEMISTRY
DEPENDS ON THE TYPE OF THE INVOLVED CARBENIUM IONS AND THE NUMBER
ARE MADE
OF SINGLE EVENTS WHICH EQUALS THE RATIO OF THE GLOBAL SYMMETRY
NUMBER OF REACTANT AND ACTIVATED COMPLEX
NUM
!CQUISITION OF KINETIC DATA
4HE AMOUNT OF EFFORT THAT SHOULD BE PUT INTO THE THEORETICAL
ASPECT OF A KINETIC INVESTIGATION DEPENDS ON THE COMPLEXITY OF
THE REACTION SCHEME THE NON
LINEARITY OF THE DEPENDENCIES
OF THE VARIABLES AND THE RELIABILITY OF THE REQUIRED KINETIC
MODEL 4HIS IS OF COURSE THE TECHNICAL DRIVER !LSO TO CONSIDER
IS THE ULTIMATE ESTIMATED PRODUCT VALUE AND THE PROBABLE COST
OF NON
CONFORMANCE OF THE KINETICS lNANCIAL SAFETY HEALTH
AND ENVIRONMENT !S NOTED ABOVE ONLY OCCASIONALLY DOES
INDUSTRY DEVELOP COMPLEX KINETIC MODELS
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
ARGE
OF NUMBER OF EXPERIMENTS IS PARAMOUNT )NTERESTINGLY
ENGINEERING COMPANIES ARE MOST LIKELY TO USE INTRINSIC KINETICS
WHILE CATALYST COMPANIES FAVOR THEM LEAST 3IGNIlCANTLY THERE
IS NO EVIDENCE FOR SIGNIlCANT USE OF MECHANISTIC OR AB INITIO
MODELS
3ELECTION OF EXPERIMENTAL REACTOR
!NY KINETIC INVESTIGATION SHOULD START WITH A SEARCH OF THE
EXISTING KNOWLEDGE CONCERNING THE REACTION SYSTEM !RMED
WITH THE INFORMATION AVAILABLE FROM THE LITERATURE AND THE
START OF A CONCEPTUAL MODEL OF THE KINETICS IT IS POSSIBLE TO
START CONSIDERING THE EXPERIMENTAL APPROACH THE EQUIPMENT
TO USE AND THE EXPERIMENTAL CONDITIONS AND PROGRAM
4HE INITIAL STEP IS USUALLY TO CONSIDER THE TYPE OF REACTOR
TO BE USED )N MANY STUDIES IT MAY BE EXPEDIENT TO USE MORE
THAN ONE TYPE 4ABLES GIVE OVERVIEWS OF SOME POSSIBLE
LABORATORY REACTORS FOR KINETIC DATE MEASUREMENT FOR GASn
SOLID AND GASnLIQUIDnSOLID SYSTEMS RESPECTIVELY !LSO GIVEN
ARE SOME OF THE IMPORTANT CHARACTERISTICS OF THOSE REACTORS
'ASnSOLID REACTIONS
.O SINGLE REACTOR IS RIGHT FOR ALL SYSTEMS AND THEREFORE A
PLURALITY OF TYPES EXISTS AS DEMONSTRATED BY 4ABLE WHICH
NUMBER OF KINETIC PARAMETERS &UNDAMENTAL MODEL FOR HYDROCRACKING
7HEN ONLY SECONDARY AND TERTIARY CARBENIUM IONS ARE CONSIDERED
GAS PHASE
PHYSISORPTION
ZEOLITE
DE PROTONATION
DE
HYDROGENATION
METAL SITES
ACID SITES
THE ABOVE ASSUMPTIONS REDUCE THE NUMBER OF DIFFERENT TYPES OF
ALKYL SHIFT
RING ALKYL SHIFTS 0#0 BRANCHINGS RING CONTRACTIONS ACYCLIC
0#0
BRANCHING
B SCISSIONS ENDOCYCLIC B SCISSIONS AND EXOCYCLIC B SCISSIONS
ELEMENTARY REACTIONS TO 4HIS INCLUDES ALKYL SHIFTS INTRA
!SSUMING QUASI EQUILIBRIUM OF THE DE HYDROGENATIONS AND THAT
THE CONCENTRATION OF CARBENIUM IONS CAN BE NEGLECTED COMPARED TO
THE TOTAL CONCENTRATION OF ACID SITES LEADS TO THE CORRESPONDING RATE
SCISSION
EQUATIONS IN &IGURE
-ODEL PARAMETERS
"OTH THERMODYNAMIC AND KINETIC PARAMETERS ARE PRESENT IN THE RATE
&IGURE (YDROCRACKING REACTION MECHANISM
EQUATIONS
L 4HE DEHYDROGENATION EQUILIBRIUM COEFlCIENT +DEH CAN BE
CALCULATED FROM TABULATED THERMODYNAMIC DATA
L 4HE PHYSISORPTION EQUILIBRIUM COEFlCIENT +, AS WELL AS THE
PARAMETERS TO BE ESTIMATED
KCOMP K + PROT !COMP EXP
SORPTION CAPACITY #SAT DEPEND ON THE CATALYST AND HAVE TO
%COMP
ACT
BE DETERMINED EXPERIMENTALLY PREFERABLY INDEPENDENTLY FROM
24
THE EXPERIMENTS AIMED AT THE DETERMINATION OF THE KINETIC
%COMP
ACT %ACT $(PROT
PARAMETERS ;VIII=
CALCULATED VIA THERMODYNAMIC DATA
EQUILIBRIUM COEFlCIENTS FOR PROTONATION +PROT (ENCE IT IS NOT
DETERMINED BY .(
40$
R
L 4HE RATE COEFlCIENTS K ONLY APPEAR COMBINED WITH THE
#CAT #T K +PROT +DEH +, P(# P(
+
, P(#
THEIR INDIVIDUAL VALUE BUT ONLY THAT OF THE PRODUCT K+PROT THE
COMPOSITE RATE COEFlCIENT WHICH AFFECTS THE REACTION RATES /F
COURSE THE LATTER SHOULD SHOW AN !RRHENIUS DEPENDENCY ON
TEMPERATURE
DETERMINED BY PHYSISORPTION EXPERIMENTS
L 4HE COMPOSITE PRE EXPONENTIAL !RRHENIUS FACTOR !COMP CAN BE
CALCULATED WITHOUT THE REGRESSION OF KINETIC DATA BASED ON
TRANSITION STATE THEORY AND ON THE PRE EXPONENTIAL FACTOR OF THE
&IGURE (YDROCRACKING 2ATE %QUATIONS (# HYDROCARBON
PHYSISORPTION EQUILIBRIUM COEFlCIENT ;IX X=
&IGURE 2EACTION SCHEME OF THE ($. OF ORTHOPROPYLANILINE /0!
SEE NEXT
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
/VERVIEW OF CHARACTERISTICS OF SEVERAL TYPES OF GASnSOLID REACTORS WHICH CAN BE USED TO
SELECT THE REACTOR TO CARRY OUT THE KINETIC EXPERIMENTS
'n3 REACTOR
DIFFERENTIAL lXED BED
INTEGRAL lXED BED
ENTRAINED
mOW REACTOR
RECYCLEGRADIENTLESS lXED BED
)NVESTIGATION
+INETICS
)SOTHERMICITY
$EACTIVATING
4YPICAL
&AST
#OSTS
OF FAST
AT HIGH
CATALYSTS
PARTICLE
EXPERIMENTATION
LOW HIGH
REACTIONS
CONVERSIONS
SIZE ;MM=
n
n
n
THERMAL GRAVIMETRIC ANALYSIS
DIFFERENTIAL mUIDIZED BED
n
PULSE lXED BED
n
TEMPORAL ANALYSIS OF PRODUCTS
n
n
TEMP PROGRAMMED REACTOR
(ENCE COMPOSITE ACTIVATION ENERGIES %COMP HAVE TO BE
ESTIMATED IE OBTAINED BY REGRESSION OF KINETIC DATA -ARTENS ET
AL ;IX X= OBTAINED SUCH A SET OF PARAMETERS BY REGRESSION OF DATA
OBTAINED ON 0T53 9 ZEOLITES AND FEEDING PURE COMPONENTS SUCH
AS N ALKANES IN THE RANGE # TO # AND CYCLOALKANES SUCH AS
METHYLCYCLOHEXANE ETHYLCYCLOHEXANE AND N BUTYLCYCLOHEXANE TO
4OTAL CONVERSION
4ABLE
A CONTINUOUS STIRRED TANK REACTOR #342 AT PRESSURES FROM
TO -0A MOLAR HYDROGEN TO HYDROCARBON RATIOS FROM TO
KG S MOL
7&
AND TEMPERATURES FROM TO + !T THESE CONDITIONS THE
&IGURE A #ONVERSION VS SPACE TIME + BAR INLET ( TO N DODECANE
HYDROCARBONS ARE IN A GASEOUS STATE )N TOTAL MORE THAN DATA
MOLAR RATIO
SPACE TIME RELATION AND &IGURE B SHOWS THE EFFECT OF CONVERSION ON
THE PRODUCT DISTRIBUTION FOR N
DODECANE AT ONE SET OF CONDITIONS )N
VIEW OF THE AMOUNT OF EXPERIMENTAL DATA THE NUMBER OF ADJUSTABLE
PARAMETERS IS RATHER LIMITED 4HIS AMONG OTHER THINGS IS DUE TO
THE ASSUMED INDEPENDENCE OF THE LATTER ON THE HYDROCARBON CHAIN
LENGTH 4HE LATTER IS TOTALLY ACCOUNTED FOR VIA THE PHYSISORPTION
PARAMETERS #SAT AND +,
ISOMERIZATION
CRACKING CONVERSION
WERE REGRESSED @&IGURE A SHOWS A TYPICAL CONVERSION VERSUS
ISOMERIZATION
CRACKING
4HE ADEQUATE MATHEMATICAL DESCRIPTION OF CONVERSIONS AND
TOTAL CONVERSION
SELECTIVITIES ON A GIVEN CATALYST AS DISCUSSED TILL NOW IS CERTAINLY
&IGURE B )SOMERIZATION AND CRACKING CONVERSION VS TOTAL CONVERSION FOR ALL
AN IMPORTANT GOAL OF KINETIC MODELING 4HE CAPABILITY OF TAKING INTO
EXPERIMENTAL CONDITIONS SYMBOLS EXPERIMENTAL CURVES MODEL PREDICTIONS
EVEN MORE IMPORTANT FEATURE OF THE HYDROCRACKING MODEL PRESENTED
HERE
)NDEED THE RATE EQUATIONS CONTAIN TWO PARAMETERS RELATED TO THE
CATALYST THE TOTAL CONCENTRATION OF ACID SITES #T AND THE STANDARD
PROTONATION ENTHALPY $(OPROT 4HE LATTER IS A MEASURE OF THE AVERAGE
STRENGTH OF THE ACID ;XI XII= !DJUSTING ONLY THESE TWO PARAMETERS AND
THE HYDROCRACKING ON 53 9 ZEOLITES WITH A DIFFERENT AVERAGE ACID
STRENGTHS CAN BE MODELED ADEQUATELY
MASS FLUX KG S M
ACCOUNT THE KINETICALLY RELEVANT PROPERTIES OF THE CATALYST IS AN
RESIDUE
MIDDLE DISTILLATE
,0'
NAPHTHA
AXIAL POSITION M
&IGURE -ASS mUXES OF MAJOR PRODUCT FRACTIONS AS A FUNCTION OF AXIAL REACTOR
COORDINATE AT TYPICAL INDUSTRIAL CONDITIONS FEEDSTOCK HYDROGENATED VACUUM GASOIL ;XIII=
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
/VERVIEW OF CHARACTERISTICS OF SEVERAL TYPES OF GASnLIQUIDnSOLID REACTORS
WHICH CAN BE USED TO SELECT THE REACTOR TO CARRY OUT THE KINETIC EXPERIMENTS
'n,n3 REACTOR
)NVESTIGATION OF
)NVESTIGATION OF
FAST REACTIONS
SEQUENTIAL REACTIONS
$EACTIVATING 4YPICAL RESIDENCE 4YPICAL CATA
CATALYSTS
TRICKLE BED
UPmOW PACKED BED
S
n
MIN
n
SPINNING BASKET
n MIN
INTERNAL RECIRCULATION REACTOR
n MIN
SLURRY REACTOR SEMI BATCH
n HR
n
SLURRY REACTOR CONTINUOUS
n MIN
n
BUBBLE COLUMN
MIN
GAS LIFT REACTOR
MIN
TIME LIQUID
&AST
#OSTS
LYST SIZE ;MM= EXPERIMENTATION LOW HIGH
WETTED WALL
S
NOT APPLIC
PULSE TRICKLE BED
S
n
PULSE SLURRY REACTOR
MIN
n
4ABLE
!PPLICATION TO THE HYDROCRACKING OF A HYDROGENATED VACUUM GASOIL
)NDUSTRIALLY HYDROCRACKING IS PERFORMED IN AN ADIABATIC lXED BED
CONDITIONS 4HE CARBON NUMBER OF THE FEED RANGES FROM TO
REACTOR CONSISTING OF THREE PHASES THE lXED CATALYTIC BED AND A
4HE RESIDUE CONSISTS OF THE HYDROCARBON FRACTION WITH OR
mOW OF GAS AND OF LIQUID )N THE TRICKLE mOW REGIME THE LIQUID mOWS
MORE CARBON ATOMS .OTE THAT THE LUMPING INTO ,0' NAPHTHA
DOWN DISPERSED IN THE FORM OF DROPLETS AND RIVULETS CONCURRENTLY WITH
MIDDLE DISTILLATES AND RESIDUE IS ONLY PERFORMED FOR REPRESENTATION
THE CONTINUOUS GAS PHASE #LEARLY THIS IS QUITE A DIFFERENCE WITH
PURPOSES 4HE KNOWLEDGE OF THE KINETICS OF THE TYPES OF
THE HYDRODYNAMICS IN THE #342 SET UP USED FOR THE DETERMINATION
ELEMENTARY REACTIONS ALLOWS US TO DESCRIBE THE VACUUM GASOIL
OF THE REACTION KINETICS 0ROVIDED THAT THE LATTER CORRESPONDS TO
CONVERSION AND THE RESULTING PRODUCT DISTRIBUTION UP TO THE LEVEL OF
INTRINSIC KINETICS IE REmECT ONLY CHEMICAL AND HENCE SCALE
THE INDIVIDUAL MOLECULES /F COURSE SUCH A DEGREE OF PRECISION IS
INDEPENDENT PHENOMENA THEIR APPLICATION TO INDUSTRIAL HYDROCRACKING
NEITHER REALLY REQUIRED NOR ATTAINABLE 4HE MAJOR BOTTLENECK CONSISTS
IS STRAIGHTFORWARD )T SUFlCES TO SUBSTITUTE THE RATE EQUATIONS IN
OF THE LACK OF MOLECULAR INFORMATION PROVIDED BY TODAYS STATE OF
THE REACTOR MODEL EQUATIONS ACCOUNTING FOR THE TRICKLE mOW IN AN
THE ART ANALYTICAL TECHNIQUES "UT AGAIN AS THE FUNDAMENTAL KINETIC
APPROPRIATE WAY 4HE LATTER CONSISTS OF THE CONSERVATION LAWS FOR
MODEL CONTAINS INFORMATION UP TO THE MOLECULAR LEVEL RELUMPING
MASS ENERGY AND MOMENTUM
CAN OCCUR TO AN EXTENT DEEMED APPROPRIATE &IGURE ILLUSTRATES THIS
&IGURE SHOWS THE EVOLUTION OF THE DIFFERENT PRODUCT FRACTIONS AS THE
BY SHOWING THE EVOLUTION OF THE LIQUID CONCENTRATION OF COMPONENTS
VACUUM GASOIL STREAMS THROUGH THE CATALYST BED AT TYPICAL INDUSTRIAL
CONSTITUTING A FRACTION OF THE RESIDUE THE MONOCYCLIC NAPHTHENIC
LIQUID CONCENTRATION MOLM
LUMPS WITH CARBON NUMBER BETWEEN AND
MO.
MO.
MO.
MO.
MO.
MO.
MO.
MO.
MO.
MO.
AXIAL POSITION M
&IGURE "REAKDOWN OF THE MONOCYCLIC NAPHTHENE FRACTION OF THE RESIDUE AS A FUNCTION OF THE AXIAL REACTOR COORDINATE ;XIII=
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
&IGURE 3IX TUBE MICRO REACTOR INSTALLATION REPRODUCED COURTESY OF 3YNETIX
IS A SUMMARIZED VERSION %ASILY THE MOST COMMON FORM
OF REACTOR FOR MEASURING KINETICS OVER A STATIONARY CATALYST
IS THE lXED BED MICROREACTOR 4HESE CAN BE OPERATED IN
DIFFERENTIAL FORM VIZ LOW CONVERSION OR IN INTEGRAL
MODE AT HIGHER CONVERSIONS 4HE lXED BED MICROREACTORS ARE
ESSENTIALLY SMALL TUBULAR REACTORS SAY n MM INCH
IN DIAMETER OPERATED WITH DIFFERENT CATALYST VOLUMES AND
SPACE VELOCITIES TO OBTAIN EITHER THE VERY LOW OR RELATIVELY HIGH
CONVERSIONS REQUIRED -ICROREACTORS ARE NOW WELL ESTABLISHED
AND THE BEST ARE FULLY AUTOMATED WITH MORE THAN ONE REACTOR
TUBE OPERATING IN PARALLEL SEE &IGURE
4HE THIRD CLASSIC CONlGURATION IS THE WELL MIXED OR
GRADIENTLESS REACTOR TYPIlED BY THE "ERTY AND #ARBERRY TYPE
REACTORS "ECAUSE THE REACTOR IS WELL MIXED THE REACTOR IS
EFFECTIVELY AT THE EXIT CONCENTRATION )N THE CASE OF A "ERTY
REACTOR SEE &IGURE A TURBINE TYPE IMPELLER DRIVES THE
GAS THROUGH THE CATALYST !N ALTERNATE DESIGN THE #ARBERRY
REACTOR HAS THE CATALYST IN A CROSS ROTATING BASKET THAT ITSELF
ACTS AS THE IMPELLER
4HESE THREE CONlGURATIONS OR OPERATING APPROACHES ARE
COMPARED IN &IGURE IN TERMS OF THE RELATIONSHIP BETWEEN
THE RATE AND THE CONVERSION 4HE FUNDAMENTAL DIFFERENCE
BETWEEN THE DIFFERENTIAL REACTOR AND THE GRADIENTLESS REACTOR
LIES IN THE FACT THAT IN THE DIFFERENTIAL REACTOR WITH LOW
CONVERSIONS THE REACTOR IS PREDOMINANTLY AT THE FEED
COMPOSITION WHEREAS FOR THE RECYCLE REACTOR ASSUMING PERFECT
MIXING THE CONCENTRATION IN THE REACTOR APPROXIMATES TO THE
EXIT CONCENTRATION 4HEREFORE THE REACTORS FUNDAMENTALLY
MEASURE THE KINETICS UNDER DIFFERENT PROCESS CONDITIONS
REGARDING COMPOSITION AND CONVERSION
4HE lXED BED MICROREACTORS AND THE GRADIENTLESS VERSION
ARE THE WORKHORSES OF GAS PHASE HETEROGENEOUS CATALYTIC
KINETICS 4HERE IS HOWEVER AN INCREASING NUMBER OF
ALTERNATIVES SOME OF WHICH ARE PARTICULARLY SUITED TO
SPECIlC PROBLEMS )F A CATALYST MASS CHANGE DUE TO THE
REACTION YIELDS IMPORTANT KINETIC INFORMATION ONE COULD
SELECT A REACTOR CAPABLE OF ON LINE MASS MEASUREMENT
4HERMO GRAVIMETRIC ANALYSIS 4'! IS NOW A WELL ESTABLISHED
TECHNIQUE BUT CONSIDER ALSO THAT THE TAPERED ELEMENT
OSCILLATING MICROBALANCE 4%/- WHICH HAS MUCH BETTER
GASnSOLID MASS TRANSFER CHARACTERISTICS THAN THE 4'!
DUE TO THE FORCED mOW THROUGH A SMALL PACKED BED ;=
4HE 4%/- HAS BEEN SUCCESSFULLY USED TO MEASURE COKE
DEPOSITION KINETICS ; = AND CHANGING OXIDATION STATES OF
OXIDE CATALYSTS ;= )F AN IMPORTANT PART OF THE KINETIC
INFORMATION CAN BE DERIVED FROM CALORIMETRY DIFFERENTIAL
SCANNING CALORIMETRY $3# COULD BE OF INTEREST )N lNE
CHEMICALS CALORIMETER REACTORS ARE BECOMING INCREASINGLY
POPULAR PARTLY BECAUSE THEY PROVIDE THE KEY INFORMATION FOR
SAFETY IN ADDITION TO THE RATE DATA
&IGURE $IAGRAM OF A "ERTY TYPE INTERNAL RECYCLE REACTOR 2EPRODUCED
COURTESY OF !UTOCLAVE %NGINEERS
INTEGRAL
& #
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
DIFFERENTIAL
RECYCLE GRADIENTLESS
& #
& #
# CONCENTRATION
# CONCENTRATION
# CONCENTRATION
, DISTANCE THROUGH REACTOR
, DISTANCE THROUGH REACTOR
, DISTANCE THROUGH REACTOR
$# # #
#
#
#
R t $# 7&
R t D#D7
R t $# 7&
$# SMALL
$# R& D7
$# LARGE
&IGURE #OMPARISON OF COMMON LABORATORY mOW MICROREACTORS USED FOR KINETIC MEASUREMENTS
&OR CASES WHERE THE CHOICE IS NOT SO CLEAR 4ABLE CAN BE
USED AS A GUIDELINE FOR THE CHOICE OF THE REACTOR &ROM THE
TABLE IT FOLLOWS THAT IMPORTANT QUESTIONS TO BE ANSWERED ARE
I !RE THE REACTIONS RELATIVELY FAST
II )S KINETIC DATA NEEDED AT HIGH CONVERSIONS CAN BE
OBTAINED RELATIVELY EASY IN A RECYCLE REACTOR
III !RE THE REACTIONS STRONGLY EXO
OR ENDOTHERMIC AND
IV $OES THE CATALYST DEACTIVATE SIGNIlCANTLY
/THER ASPECTS MAY ALSO INmUENCE THE CHOICE SUCH AS THE
APPROACH TO IDEAL PLUG mOW OR MIXING THE RISK OF mOW
MALDISTRIBUTION THE EASE OF MEASUREMENT OF THE CATALYST
TEMPERATURE AND THE EASE OF WITHDRAWING SAMPLES 4HE
AVAILABLE CATALYST SIZE THE ALLOWABLE REACTOR COSTS AND THE
EXPERIMENTAL EFlCIENCY AMOUNT OF KINETIC DATA PER UNIT OF
TIME OF EXPERIMENTATION WILL DETERMINE THE lNAL CHOICE
2EACTORS OPERATED AT STEADY
STATE ARE EXPERIMENTALLY THE
MOST CONVENIENT BUT THE DYNAMICALLY OPERATED SYSTEMS ARE
NOW RECEIVING INCREASING ATTENTION 4HESE INCLUDE THE PULSED
lXED BED TEMPORAL ANALYSIS OF PRODUCTS 4!0 AND TEMPER
ATURE
PROGRAMMED REACTORS MENTIONED IN 4ABLE (OWEVER
WHILE THEY DO ALLOW FAST ACQUISITION OF KINETIC DATA IT IS NOT
ALWAYS CLEAR HOW TO TRANSLATE THOSE DATA INTO A MATHEMATICAL
MODEL 4HEY OFTEN ALSO REQUIRE A MORE SKILLED OR EXPERIENCED
OPERATOR OR A SIGNIlCANTLY LONGER LEARNING PERIOD )N GEN
ERAL THESE REACTORS ARE MAINLY OF INTEREST FOR EXTENSIVE KINETIC
INVESTIGATIONS INCLUDING ELUCIDATION OF MECHANISTIC ASPECTS
4HE lNAL CHOICE OF THE REACTOR IS USUALLY DETERMINED BY THE
FOLLOWING ASPECTS
v !BSOLUTE REACTION RATE
v #ATALYST SHAPE AND SIZE
v 4HE REACTORS ALREADY AVAILABLE IN THE LABORATORY OR THE
RELATIVE COSTS OF THE ALTERNATIVE NEW INSTALLATIONS
v ,IKELIHOOD OF SIGNIlCANT TRANSPORT LIMITATIONS MASS AND
HEAT TRANSFER
v .ONIDEALITIES SUCH AS mOW DISTRIBUTION AND HYDRO
DYNAMICS
)F POSSIBLE ANY COMPLICATIONS ARISING FROM NONKINETIC
PARAMETERS IMPINGING ON THE OBSERVATION OF INTRINSIC KINETICS
SHOULD BE CIRCUMVENTED BY CHOOSING PROPER TEST CONDITIONS
&IGURE $IAGRAM OF A 2OBINSONn-AHONEY REACTOR 2EPRODUCED COURTESY OF
!UTOCLAVE %NGINEERS
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
&IGURE !LTERNATE REACTORS FOR MULTIPHASE KINETICS MEASUREMENTS A TURBINE REACTOR B SCREW IMPELLER STIRRED REACTOR
'ASnLIQUIDnSOLID REACTIONS
4HE CHOICE OF THE REACTOR FOR INVESTIGATION OF THE KINETICS
OF GASnLIQUIDnSOLID SYSTEMS IS USUALLY DETERMINED BY THE
CHARACTERISTICS SHOWN IN 4ABLE &OR THOROUGH KINETIC
INVESTIGATIONS IN WHICH THE INmUENCE OF THE REACTION PRODUCTS
AND SEQUENTIAL REACTIONS SHOULD ALSO BE INVESTIGATED ONLY
THE SLURRY REACTOR AND THE INTERNAL RECIRCULATION REACTOR ARE
TRULY RECOMMENDED 4HE SLURRY REACTOR MOST COMMONLY
ALMOST INEVITABLY TAKES THE FORMAT OF A STIRRED
AUTOCLAVE )F NOT PROPERLY ASSESSED THESE SYSTEMS CAN EASILY
BE PRONE TO MASS TRANSPORT LIMITATIONS PARTICULARLY AT
THE GASnLIQUID INTERFACE ! COMMONLY USED TYPE OF GASn
LIQUIDnSOLID GRADIENTLESS INTERNAL RECIRCULATION REACTOR IS THE
2OBINSONn-AHONEY REACTOR SEE &IGURE WHERE THE GASn
LIQUID DISPERSION IS FORCED THOUGH A CATALYST BASKET 4WO
ALTERNATIVE TYPES OF INTERNAL RECIRCULATION REACTORS HAVE BEEN
PROVEN SUCCESSFUL FOR KINETIC INVESTIGATIONS THE TURBINE
REACTOR IN WHICH THE GASnLIQUID MIXTURE IS TRANSPORTED BACK
TO THE TOP BY TURBINE BLADES LOCATED IN THE OUTER ANNULAR OF
THE REACTOR;= AND THE SCREW IMPELLER STIRRED REACTOR 3)32
HAVING THE SCREW IN THE CENTRAL SHAFT ;= "OTH REACTORS ARE
SHOWN IN &IGURE
3ELECTION OF EXPERIMENTAL CONDITIONS
)T IS EVIDENT THAT THE REACTOR AND ANALYTICAL EQUIPMENT
GENERALLY LIMIT THE RANGE OF THE EXPERIMENTAL CONDITIONS THAT
CAN BE COVERED (OWEVER SEVERAL ADDITIONAL ASPECTS MAY
FURTHER LIMIT THE RANGES OF CONDITIONS AT WHICH USEFUL
KINETIC DATA CAN BE OBTAINED )F INTRINSIC KINETICS ARE TO
BE ASSURED IT IS ESSENTIAL TO CHECK ON RATE LIMITATION DUE
TO MASS AND HEAT TRANSPORT LIMITATIONS /NE SHOULD ALSO
CHECK FOR OTHER PHENOMENA CAUSING NONIDEALITY SUCH AS
AXIAL DISPERSION IN A TUBULAR REACTOR CATALYST BYPASS AND
INADEQUATE MACROMIXING 4HERE ARE SEVERAL hTRICKSv USED TO
GENERATE CONDITIONS WHERE TRANSPORT IS NOT LIMITING 4HE
MOST COMMON OF THESE IS THE USE OF INERT PARTICLES MIXED
IN WITH THE CATALYST TO ARTIlCIALLY INCREASE THE ACTIVE REACTOR
BULK VOLUME 4HIS DILUTES ANY HEAT EFFECTS AND BY DILUTION
WITH lNE PARTICLES AXIAL DISPERSION AND BYPASSING CAN BE
LIMITED EVEN FOR A COMBINATION OF A RELATIVELY SHORT BED AND
INDUSTRIAL CATALYST PARTICLE SIZE )F THE PROBLEM IS INTRA
PELLET
THEN THE ONLY OPTION IS TO OPERATE WITH A SMALLER PARTICLE SIZE
4ABLES AND GIVE AN INDICATION OF SUITABLE CATALYST
SIZE AND SHAPE SUCH AS POWDER SMALL CRUSHED PARTICLES
AND COMPLETE CATALYST BODIES )F INTRINSIC KINETICS ARE TO BE
-EASUREMENT OF KINETICS IN INDUSTRY
)T IS TIME NOW TO RETURN TO THE INDUSTRIAL SURVEY 4HE RESULTS
ARE FAIRLY EMPHATIC !LL COMPANIES DO EMPLOY IN
HOUSE TEST
UNITS FOR MEASURING KINETIC DATA ALTHOUGH MANY ALSO DO
KINETIC WORK IN COLLABORATION WITH ACADEMIC INSTITUTIONS AND
RESEARCH ORGANIZATIONS WITH OF REPLIES CITING THE USE
OF EXTERNAL DATA !LL RESPONDENTS CITE THE USE OF lXED BED
MICROREACTORS WHICH COMES AS NO SURPRISE 4HE USE OF PILOT
PLANT FOR MODEL lTTING IS COMMON PLACE BUT ONLY USE
FULL
SCALE PLANT OPERATING DATA FOR THIS PURPOSE
!S REGARDS LABORATORY REACTOR TYPES HOWEVER UTILIZATION
IS LESS WIDESPREAD /NLY CITE THE USE OF RECYCLED
OR GRADIENTLESS REACTORS WHILE AS FEW AS HAVE
USED TEMPERATURE PROGRAMMED TECHNIQUES AND ONLY ONE
RESPONDING COMPANY POSSESSED A 4!0 REACTOR
4HESE DATA ARE A FEW YEARS OLD NOW BUT IN TRUTH LITTLE
HAS REALLY CHANGED )NDUSTRY STILL RELIES HEAVILY ON lXED BED
MICROREACTORS FOR GAS PHASE REACTIONS ALMOST TO THE POINT OF
EXCLUSIVITY 'IVEN THE IMPROVEMENT IN THE TECHNIQUES NOW
ONGOING IN ACADEMIA THERE IS CLEARLY HEADROOM WHICH SHALL
BE ADDRESSED LATER
)T IS ALSO APPARENT FROM THE SURVEY THAT INDUSTRY DOES
NOT BELIEVE IT IS AS CAREFUL AS IT SHOULD BE IN SELECTING
EXPERIMENTAL CONDITIONS 4HE ABSENCE OF MASS TRANSFER
LIMITATION IS NORMALLY CHECKED AT LEAST EXPERIMENTALLY 0LUG
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
MEASURED THE PRECISE CATALYST SIZE TO BE USED SHOULD BE
ESTIMATED VIA CALCULATIONS CONCERNING TRANSPORT LIMITATIONS
AND OTHER PHENOMENA POSSIBLY CAUSING NONIDEALITIES !S
NOTED ABOVE IF LARGE CATALYST PELLETS ARE TO BE USED IN PRAC
TICE IT MAY BE EXPEDIENT TO USE FULL
SIZED PELLETS OFTEN
DILUTED WITH INERT PARTICLES AND MEASURE THE APPARENT KINET
ICS WITH THE KNOWLEDGE THAT THE DATA WILL INCLUDE INTRA
PELLET
TRANSPORT EFFECTS
4HE EXPERIMENTAL REQUIREMENT FOR INTRINSIC KINETICS IS A
MAJOR AREA OF STUDY IN ITS OWN RIGHT AND ANYTHING MORE THAN
A STATEMENT OF AWARENESS IS BEYOND THE SCOPE OF THIS PAPER
4HERE IS A CONSIDERABLE WEALTH OF LITERATURE AVAILABLE IN THIS
lELD SEE FOR EXAMPLE +APTEIJN -OULIJN ;= OR &ROMENT
"ISCHOFF ;=
/NCE THE RANGE OF SUITABLE CONDITIONS IS SET A CHOICE
HAS TO BE MADE FOR THE NUMBER OF EXPERIMENTS AND THE
SETS OF CONDITIONS AT WHICH THESE SHOULD BE CARRIED OUT
&ROM A MECHANISTIC POINT OF VIEW IT OFTEN IS ASSUMED THAT
MOST RELIABLE RESULTS WILL BE OBTAINED WHEN VARYING THE
INDEPENDENT VARIABLES JUST ONE BY ONE (OWEVER A STATISTICAL
APPROACH WILL FREQUENTLY INCREASE EXPERIMENTAL EFlCIENCY BY
VARYING MORE THAN ONE INDEPENDENT VARIABLE SIMULTANEOUSLY
/F COURSE THIS HAS THE DISADVANTAGE THAT EVALUATION OF THE
DATA BY VISUAL INSPECTION RATHER THAN BY STATISTICAL ANALYSIS
BECOMES HARDER %XPERIMENTAL DESIGN IS ALSO A LARGE lELD
AND BEYOND THE SCOPE OF THE CURRENT PAPER !T ITS SIMPLEST
THIS IS EPITOMIZED BY FACTORIAL DESIGN ALTHOUGH MORE
SOPHISTICATED TECHNIQUES ARE AVAILABLE WHICH ARE NONLINEAR IN
THEIR APPROACH ; =
mOW AND ISOTHERMICITY ARE FREQUENTLY ASSUMED WITHOUT ANY
SUCH VERIlCATION THE USE OF RIGOROUS MODELS TO DESCRIBE
THE MICROREACTOR IS RARE 4HE GOAL SHOULD BE SIMPLE REACTORS
THAT REQUIRE ONLY SIMPLE MODELS )N MORE COMPLEX MIXING
SITUATIONS SUCH AS MULTIPHASE AND mUIDIZED SYSTEMS THE USE
OF COLD mOW MODELS FOR THE HYDRODYNAMICS AND MASS TRANSFER
IS RARE
#OLLECTIVELY THEREFORE INDUSTRY BELIEVES IT IS MAYBE NOT
AS DILIGENT AS IT SHOULD BE IN ENSURING THE INTRINSIC NATURE
OF ITS KINETICS 4HIS IS ALMOST CERTAINLY MITIGATED BY AN
ENORMOUS ACCUMULATED EXPERIENCE IN TRANSLATING LABORATORY
DATA INTO KINETIC MODELS AND USING THESE TO ACCURATELY AND
SAFELY PREDICT THE PERFORMANCE OF A COMMERCIAL REACTOR
+INETIC MODELING
7HEN A SERIES OF EXPERIMENTS HAS BEEN CARRIED OUT IT IS THEN
NECESSARY TO DEVELOP ONE OR MORE KINETIC MODELS AND TO
TRY TO ADJUST THE KINETIC PARAMETERS BY lTTING THE MATHEMAT
ICAL EXPRESSIONS TO THE EXPERIMENTAL DATA 4HE AMOUNT OF
WORK REQUIRED FOR THIS IS OFTEN SIGNIlCANTLY UNDERESTIMATED
BECAUSE OF UNEXPECTED COMPLICATIONS #OMMON hCOMPLICA
TIONSv ON THE CHEMICAL SIDE ARE LOW
LEVEL IMPURITIES IN THE
FEED UNEXPECTED SIDE REACTIONS AND UNCERTAINTIES CONCERN
ING THE PHYSICAL PROPERTIES OF THE MIXTURE OR OF SOME OF
THE COMPOUNDS PRESENT %XAMPLES ON THE EXPERIMENTAL SIDE
ARE RESIDUES OF CHEMICALS IN THE REACTOR FROM PREVIOUS WORK
REACTOR WALLS TAKING PART IN THE REACTION DIFlCULTIES WITH
CHEMICAL ANALYSIS AND INACCURACIES OF THE ANALYTICAL EQUIP
MENT 0ROBLEMS ALSO OCCUR WITH THE MODELING ITSELF SUCH AS
THE USE OF A KINETIC MODEL THAT IS EITHER TOO SIMPLE OR TOO
COMPLEX THE USE OF ONLY ONE OR INSUFlCIENT DIFFERENT MODELS
AND A LACK OF PHYSICOCHEMICAL BACKGROUND OF THOSE MODELS
/F COURSE KINETIC RESEARCH HAS BEEN CARRIED OUT FOR MANY
YEARS AND ACCORDINGLY THERE IS MUCH EXPERIENCE AVAILABLE IN
THE LITERATURE AND IN MANY LABORATORIES REGARDING SUITABLE
APPROACHES FOR DIFFERENT PROBLEMS RECOMMENDATIONS TO
IMPROVE THE ACCURACY OF MODELS WAYS TO ENHANCE THE ENTIRE
INVESTIGATION AND LAST BUT NOT LEAST A FEW PITFALLS TO AVOID !
NUMBER OF CASE STUDIES HAVE ALREADY BEEN INTRODUCED 4HESE
AND A FEW MORE WILL NOW BE USED TO TELL A FEW SALUTARY TALES
AND TO TRY AND DEMONSTRATE GOOD PRACTICE AND LEAD TO SOME
SIMPLE RECOMMENDATIONS ON KEY POINTS TO CONSIDER WHEN
DOING KINETIC MODELING
7ORK ON THE REACTION KINETICS CAN USEFULLY BEGIN EVEN
IN THE EARLIEST STAGES OF A CATALYST OR REACTOR DEVELOPMENT
PROGRAM SEE )NTERMEZZO 2ATHER SIMPLE MODELS THAT
DESCRIBE THE IMPORTANT REACTIONS REASONABLY WELL CAN BE A
RELATIVELY CHEAP BUT VERY USEFUL INPUT IN PRIMARY ECONOMIC
EVALUATIONS CONCERNING THE FULL
SCALE PRODUCTION AND THE
AMOUNT OF INVESTIGATION AND DEVELOPMENT WORK REQUIRED
!LTHOUGH KINETIC MODELING USUALLY NEEDS THE REACTION
MECHANISM PURELY AS AN INPUT TO HELP BUILD A MATHEMATICAL
DESCRIPTION OF THE EVENTS OCCURRING IT CAN ALSO LEAD TO NEW
INSIGHTS IN THE REACTION MECHANISM AND REACTION SEQUENCES
!N EXAMPLE CONCERNING THE DISCOVERY OF A NEW INSIGHT
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
INTERMEZZO
3TART YOUR KINETICS STUDIES EARLY IN THE DEVELOPMENT PROGRAM FOR MAXIMUM ADVANTAGE
#//#(
#//(
#//#(
(
#//#(
#//(
4HE T
#//#(
&IGURE 5PGRADING OF BUTADIENE
3INCE MARKET PRICES FOR BUTADIENE ARE LOW USE OF BUTADIENE
/NE OF THE OBJECTIVES OF THIS RESEARCH PROJECT WAS TO SPEED
AS FEEDSTOCK FOR THE PRODUCTION OF HIGH GRADE CHEMICALS IS VERY
UP THE COURSE OF DEVELOPMENT OF THE NEW PRODUCT AS MUCH AS
INTERESTING 4HE TELOMERIZATION REACTION OF BUTADIENE WITH O PHTHALIC
POSSIBLE 4HEREFORE KINETIC MODELING WAS STARTED CONCURRENTLY WITH
ACID YIELDS A MIXTURE OF LINEAR AND BRANCHED ESTER ISOMERS AS
THE EXPERIMENTAL OPTIMIZATION OF THE REACTION SYSTEM 4HE RESULTS OF
SHOWN IN &IGURE !FTER HYDROGENATION OF DOUBLE BONDS IN THE
THREE EXPERIMENTS IN WHICH THE BUTADIENEO PHTHALIC ACID RATIO WAS
ALKENE GROUPS THE PRODUCT HAS POTENTIAL USE AS PLASTICIZER
VARIED AND OTHER PARAMETERS KEPT CONSTANT WERE UTILIZED TO EVALUATE
4HE REACTIONS ARE HOMOGENEOUSLY CATALYZED BY A PALLADIUMnLIGAND
PROPOSED KINETIC MODELS #RITERIA FOR THE SELECTION OF THE MOST
COMPLEX IN A POLAR ORGANIC SOLVENT 4HE FORMATION OF THE PRODUCT
APPROPRIATE MODEL WERE BEST lT FOR THE CONVERSION OF O PHTHALIC
PROCEEDS THROUGH MONOESTER SPECIES 4HIS HAS BEEN CONlRMED
ACID AND SELECTIVITIES OF THE PRODUCTS USING A MINIMUM NUMBER OF
BY A COMBINATION OF EXPERIMENTATION AND KINETIC MODELING !
PARAMETERS MINIMIZE THE PRODUCT OF THE WEIGHTED SUM OF SQUARES OF
SIMPLIlED REACTION SCHEME IS SHOWN IN &IGURE
RESIDUALS AND THE NUMBER OF PARAMETERS
/
2
/
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/
2
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2
2
/
/
/
/
/
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/(
2
2
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2
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&IGURE 3IMPLIlED REACTION SCHEME
CONCERNING THE ADSORPTION MODE IN A SELECTIVE HYDROGENATION
PROCESS IS SHOWN IN )NTERMEZZO
4HE IMPORTANCE OF USING PROPER STATISTICAL TOOLS IN
THE KINETIC INVESTIGATION SHOULD NEVER BE UNDERESTIMATED
EITHER FOR REASONS OF TIME EFFECTIVENESS OR CONlDENCE IN THE
RESULTING MODEL 7HILE AT THE BASIC LEVEL THIS CAN SIMPLY
BE THE EXPERIMENTAL DESIGN FOLLOWED BY USE OF A SUITABLE
OPTIMIZATION PACKAGE FOR PARAMETER ESTIMATION IT MAY ALSO
INCLUDE MATHEMATICAL TRANSFORMATION OF THE MODEL EQUATION
!CKNOW
IN ORDER TO GIVE MORE RELIABLE lTTING )NTERMEZZO SHOWS
HOW ,((7 KINETIC EXPRESSIONS MAY BE REPARAMETERIZED
BY MATHEMATICALLY REMOVING ALL KINETIC PARAMETERS FROM
THE NUMERATOR 4HIS REPARAMETRIZATION SUPPRESSES THE
INTERDEPENDENCY BETWEEN THE PARAMETERS AND THUS ENHANCES
THE lTTING PROCESS
+INETIC MODELING GOOD PRACTICE
)N ORDER TO IMPROVE THE EFlCIENCY AND ACCURACY OF KINETIC
MODELING A SERIES OF RECOMMENDATIONS CAN BE GIVEN OF
WHICH SOME WERE ILLUSTRATED OR MENTIONED PREVIOUSLY
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
4HE TELOMERIZATION OF BUTADIENE WITH O PHTHALIC ACID
4HE PROCEDURE RESULTED IN A MODEL THAT CONSISTS OF VERY SIMPLE RATE
4HE EFFECT OF CATALYST CONCENTRATION IS INCLUDED IN THE RATE CONSTANTS
EXPRESSIONS 7HEN THE REACTANTS ARE DENOTED BY " BUTADIENE 0!
FOR A CERTAIN RANGE OF CONCENTRATIONS 4HE ROLE OF THE CATALYST IN
O PHTHALIC ACID -LINEAR LINEAR MONOESTER INTERMEDIATE AND -BRANCHED
DETERMINING SELECTIVITIES AND INHIBITION EFFECTS BY BYPRODUCTS SUCH
BRANCHED MONOESTER INTERMEDIATE THE RATE EQUATIONS ARE GIVEN
AS OCTATRIENE WAS NOT CONSIDERED IN THE MODEL 3TATISTICAL ANALYSIS
BY
OF THE MODEL SHOWED THAT THE ACCURACY OF THE PARAMETERS WOULD
R K;"= ;0!=
HAVE TO BE IMPROVED IN ORDER TO INCREASE THE RELIABILITY OF A PLANT
R K ;"= ;0!=
SCALE REACTOR DESIGN
R K ;"= ;-LINEAR=
4HE SIMPLE MODEL OBTAINED FROM EXPERIMENTS THAT WERE CONDUCTED
R K ;"= ;-LINEAR=
FOR PURPOSES OTHER THAN KINETIC MODELING IS SUITABLE FOR TWO
R K ;"= ;-BRANCHED=
REASONS
R K ;"= ;-BRANCHED=
v )NTEGRATION IN A REACTOR MODEL FOR mOW SHEET CALCULATIONS IN
R K ;"=
ORDER TO MAKE PRIMARY ECONOMIC EVALUATIONS
!N EXAMPLE OF THE COMPARISON BETWEEN EXPERIMENT AND MODEL
CALCULATIONS AFTER OPTIMIZATION OF THE KINETIC PARAMETERS IS GIVEN IN
v 3TARTING POINT FOR THE DEVELOPMENT OF A MORE SOPHISTICATED
KINETIC MODEL NEEDED FOR A lNAL REACTOR DESIGN
&IGURE )N THIS lGURE O PHTHALIC ACID ONE OF THE INTERMEDIATES
4HE CONTINUATION OF THE DEVELOPMENT OF THE KINETIC MODEL INCLUDED
AND THE LINEAR PRODUCT ARE SHOWN IN DIMENSIONLESS CONCENTRATIONS
EXPERIMENTS AT VARYING TEMPERATURES AND SPECIlCALLY IDENTIlCATION
AS A FUNCTION OF TIME ALL CONCENTRATIONS HAVE BEEN NORMALIZED TO THE
OF PRODUCT INHIBITION ADDING OCTATRIENE OR ONE OF THE ESTER PRODUCTS
INITIAL O PHTHALIC ACID CONCENTRATION
TO THE STARTING MIXTURE
CONCENTRATION DIMENSIONLESS
NTAGE
#//(
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TIME IN MINUTES
&IGURE %XPERIMENT SYMBOLS AND MODEL LINES FOR THREE SELECTED COMPONENTS
!CKNOWLEDGMENT 4HE AUTHORS ARE GRATEFUL TO *OHAN (OORN $3- 2ESEARCH 0/ "OX -$ 'ELEEN 4HE .ETHERLANDS FOR SUPPLYING THIS CASE STUDY
v 3TRIVE FOR INTRINSIC KINETICS RATHER THAN APPARENT KINETICS
WHERE THE TRANSPORT EFFECTS AND INTRINSIC KINETICS ARE
LUMPED 4HIS STRONGLY IMPROVES THE UNDERSTANDING OF
THE PHYSICOCHEMICAL BACKGROUND OF THE SYSTEM AND MAY
GIVE INSIGHT INTO UNUSUAL OR UNEXPECTED EFFECTS AND ALSO
IMPROVES THE RELIABILITY AND ACCURACY OF THE MODEL WHEN
EXTRAPOLATED
v 4HE EXPERIMENTAL REACTOR NEED NOT NECESSARILY BE A SMALL
SCALE COPY OF THE INDUSTRIAL REACTOR 4HE USE OF TRICKLE
BEDS AND mUID BEDS SHOULD PREFERABLY BE AVOIDED
v $ETERMINE IN ADVANCE WHAT KINETIC INFORMATION IS REALLY
NEEDED TAKING INTO ACCOUNT THE RESOURCES AVAILABLE
v !LWAYS SEARCH FOR INFORMATION ON COMPARABLE CHEMICAL
SYSTEMS "ESIDES LITERATURE ONE SHOULD NOT FORGET TO
CHECK IF THERE IS INFORMATION AVAILABLE IN THE LABORATORY
FROM EARLIER RESEARCH
v 5SE MORE THEORETICALLY
BASED MODELS IF RELIABILITY OF THE
KINETICS IS REQUIRED FOR EXTRAPOLATION
v !VOID ESTIMATING A LARGE NUMBER OF DIFFERENT KINETIC
PARAMETERS FROM A SMALL EXPERIMENTAL DATA SET !N
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
INTERMEZZO
+INETIC MODELING MAY CONTRIBUTE TO NEW INSIGHTS IN REACTION MECHANISMS AND REACTION
4HE REACTION NETWORK SHOWN IN &IGURE CAN DESCRIBE THE SELECTIVE
)N VIEW OF THE SAME CONVERSION RATE IT IS SPECULATED THAT
HYDROGENATION OF CINNAMALDEHYDE TO CINNAMYL ALCOHOL
THE ADSORPTION MODE AT HIGH CONCENTRATIONS DIFFERS FROM LOWER
4HE DEVELOPMENT OF THE CONCENTRATIONS OF THE VARIOUS COMPONENTS
CONCENTRATIONS COMPARABLE TO THE ADSORPTION OF SURFACTANTS IN
IN A BATCH REACTOR MAY BE WELL DESCRIBED BY A MODEL WITH lRST
THE FORM OF MICELLES )N THIS SENSE THE CINNAMALDEHYDE ADSORBS
ORDER REACTION STEPS LIKE IN )NTERMEZZO FOR ($. INCLUDING @DIRECT
PERPENDICULAR TO THE 0T SURFACE WITH THE AROMATIC RINGS IN A PARALLEL
REACTIONS FROM REACTANT TO INTERMEDIATE AND END PRODUCTS 4HIS IS
ARRANGEMENT hSELF ASSEMBLING WHICH IS SCHEMATICALLY DEPICTED
EXAMPLIlED BY &IGURE WHERE THE LINES DRAWN ARE THE KINETIC MODEL
IN &IGURE .OW THE CARBONYLIC FUNCTIONALITY WILL BE MOST PRONE
PREDICTIONS FOR LOW CONCENTRATIONS OF CINNAMALDEHYDE IN TOLUENE ;XIV=
TO HYDROGENATION ,ITERATURE ON THIS TYPE OF ORDERED ADSORPTION IS
(OWEVER AT HIGHER CONCENTRATIONS ^ MOLL THE SELECTIVITY FOR THE
SCARCE BUT SOME EXAMPLES WITH AROMATIC MOLECULES HAVE BEEN
DESIRED PRODUCT CINNAMYL ALCOHOL INCREASES CONSIDERABLY WHILE AT
REPORTED ;XVI=
THE SAME TIME THE ABSOLUTE CONVERSION RATE OF CINNAMALDEHYDE IS
4HIS STRESSES THE IMPORTANCE THAT IN SOME CASES EVEN THE ADSORPTION
ABOUT THE SAME 4HIS SELECTIVITY CHANGE CAN IN NO WAY BE PREDICTED
MODE SHOULD BE INCORPORATED IN A KINETIC MODEL OTHERWISE REACTION
BY THE LOW CONCENTRATION DERIVED KINETIC MODEL ;XV=
SELECTIVITIES WILL NOT BE PREDICTED
CINNAMYL ALCOHOL #/,
CINNAMALDEHYDE #!,
B
METHYLSTYRENE
HYDROCINNAMALDEHYDE (#!,
PHENYL
PROPANOL (#/,
PHENYLPROPANE 00
CYCLOHEXYLPROPANOL #(0
&IGURE #INNAMALDEHYDE HYDROGENATION REACTION NETWORK
v
v
v
v
APPROPRIATE USE OF STATISTICAL TOOLS FACILITATES THE REJECTION
OF KINETIC MODELS CONTAINING TOO MANY PARAMETERS
$ElNE SEVERAL DIFFERENT KINETIC MODELS THAT MAY DESCRIBE
THE SYSTEM AND MODEL SELECTION CRITERIA TO ALLOW MAKING
A CHOICE BETWEEN THESE MODELS
$ESIGN ADDITIONAL EXPERIMENTS WITH TWO GOALS I TO
FACILITATE THE SELECTION OF THE @BEST MODEL AND II TO
IMPROVE THE ACCURACY OF THE KINETIC PARAMETERS
!PPLY PROPORTIONAL WEIGHTING IN ORDER TO ACHIEVE AN
EQUALLY GOOD DESCRIPTION OF SMALL EXPERIMENTAL RESPONSE
VALUES AS FOR LARGE EXPERIMENTAL RESPONSE VALUES
!RRHENIUS AND ,((7 EXPRESSIONS CAN BENElCIALLY
BE REPARAMETERIZED ;= 4HIS STRONGLY REDUCES THE
INTERDEPENDENCY BETWEEN ACTIVATION ENERGY AND THE PRE
EXPONENTIAL FACTOR WHICH ENHANCES THE lTTING PROCEDURE
3EE )NTERMEZZO FOR MORE DETAILS
&INALLY THE RESEARCHER IN KINETICS HAS TO CHOOSE A SUITABLE
SOFTWARE PACKAGE TO PERFORM THE PARAMETER ESTIMATION
"ECAUSE SEVERAL DIFFERENT PACKAGES ARE COMMERCIALLY AVAILABLE
WITH STRONGLY VARYING CAPACITIES USER INTERFACES AND
VERSATILITY IT IS DIFlCULT TO CHOOSE THE MOST SUITABLE PACKAGE
! FUTURE PAPER;= WILL FOCUS ON ASPECTS TO BE CONSIDERED
BEFORE MAKING A CHOICE OF lTTING SOFTWARE
#ONCLUSIONS
+INETICS STUDIES IN INDUSTRY ARE PRAGMATIC %XPERIMENTS ARE
EXPENSIVE AND THERE MUST BE A lNANCIAL JUSTIlCATION FOR
KINETIC STUDIES 4HERE ALSO NEEDS TO BE A TECHNICAL JUSTIlCATION
FOR THE MODEL AND THE OVERRIDING REQUIREMENT IS TO MAINTAIN
SIMPLICITY 4HE MAJORITY USAGE OF KINETIC MODELS IS IN PROCESS
NOT CATALYSIS RESEARCH 7HILE INDUSTRY WOULD LIKE TO OBTAIN
INTRINSIC KINETICS MODELS BASED ON MECHANISTIC CONSIDERATIONS
SEQU
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
SEQUENCES 3ELECTIVE HYDROGENATION OF CINNAMALDEHYDE TO CINNAMYL ALCOHOL
(#/,
# MOL L
ACTION
#!,
(#!,
#(0
#/,
00
2ESIDENCE TIME MIN
&IGURE %XPERIMENTAL RESULTS CINNAMALDEHYDE HYDROGENATION
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#
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0T
&IGURE 3PECULATED ADSORPTION MODE OF CINNAMALDEHYDE MOLECULES ON THE CATALYST
IT IS RARELY EXPEDIENT SO TO DO DUE TO REASONS OF COST AND MAN
HOURS AS WELL AS ELAPSED TIME AND ECONOMIC AND TECHNICAL
JUSTIlCATION
"EFORE SETTING OUT ON A MODELING EXERCISE IT IS ESSENTIAL
TO THINK CAREFULLY ABOUT THE REQUIREMENTS 7HAT WILL THE
MODEL BE USED FOR !ND BY WHOM )S A FULL KINETIC MODEL
WHAT IS ACTUALLY NEEDED 7ILL THERE BE A NEED FOR EXTRAP
OLATION REGARDING OPERATING DOMAIN AS WELL AS SCALE )N
ASSEMBLING THE MATHEMATICAL EXPRESSION EVERY EFFORT SHOULD
BE MADE TO OBTAIN PHYSICOCHEMICAL BASIS "EWARE OF OVER
PARAMETERIZATION AND MAKE MAXIMUM USE OF APPROPRIATE
STATISTICAL TOOLS )N DOING ALL THIS IT IS WORTH BEARING IN
MIND THAT PROCESS MODELS DO NOT NEED DETAILED KINETICS BUT
RATHER A RELIABLE RATE MODEL %VEN WITH THIS THE INmUENCE OF
EXTERNAL FACTORS CHANGES WITH SCALE PARTICULARLY THE EFFECTS OF
MACRO MIXING AND TRANSPORT
&UTURE ACTIVITIES
)N CONSIDERING WHAT THE FUTURE HOLDS FOR KINETICS OR
MORE PRECISELY WHAT ARE THE MAIN AGENDA ITEMS FOR KINETICS
RESEARCH IT IS WORTH RETURNING AGAIN TO THE INDUSTRIAL
SURVEY 4HIS ALSO INQUIRED AS TO OPINIONS ON THE ASPECTS OF
KINETICS THAT MOST URGENTLY REQUIRE IMPROVEMENTS 4HREE
AREAS WERE COMMONLY CITED
I )MPROVEMENTS IN THE ACQUISITION OF KINETIC DATA SINCE
THIS IS CONSIDERED TOO COSTLY AND TIME
CONSUMING
II 4HERE IS CONSIDERABLE DIFlCULTY IN THE DETERMINATION AND
SUBSEQUENT APPLICATION OF KINETICS FOR THE CASE OF UNSTABLE
OR VARIABLE CATALYST PERFORMANCE EG DEACTIVATION
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
INTERMEZZO
3TATISTICAL TECHNIQUES HELP TO PERFORM EXPERIMENTAL DESIGN AND TO lND OPTIMAL KINETIC
$ESIGN OF EXPERIMENTS IS A COLLECTION OF STATISTICAL TECHNIQUES
./
EMPLOYED FOR SYSTEMATIC EXPERIMENTATION AND OPTIMAL MODEL
ANALYSIS 4HIS APPLICATION ILLUSTRATES THE USE OF EXPERIMENTAL DESIGN
FOR MODEL BUILDING AND ANALYSIS FOR THE SELECTIVE CATALYTIC REDUCTION
.(
./OUT
OF ./ BY .(
.( OUT
%XPERIMENTAL SET
UP
4HE EXPERIMENTS FOR THE DETERMINATION OF THE INTRINSIC KINETICS HAVE
BEEN PERFORMED IN A TUBULAR PACKED BED REACTOR WHICH CAN BE
:
: ,
MODELED USING THE PLUG mOW REACTOR MODEL AS SHOWN IN &IGURE
4HE SEPARATE ADSORPTION AND SURFACE REACTION STEPS HAVE BEEN
&IGURE $IFFERENTIAL REACTOR MODEL
LUMPED INTO ONE OVERALL REACTION DESCRIBING THE ./ CONVERSION
./ .( / m . (/
%ACH EXPERIMENT COVERS A SPECIlC COMBINATION OF MOLAR FRACTIONS
0OWER LAW
./ .( (/ AND / AT THE REACTOR INLET THE REACTOR TEMPERATURE
AND THE SPACE VELOCITY ! SMALL CATALYST PARTICLE SIZE HAS BEEN
A
R K P./
P.(B P(/C P/D
SELECTED TO AVOID MASS TRANSFER LIMITATIONS DUE TO PORE DIFFUSION
EFFECTS !T THE REACTOR OUTLET THE MOLAR FRACTIONS ./ AND .( HAVE
%LEY 2IDEAL
BEEN MEASURED
2ATE EXPRESSIONS
!CCORDING TO THE DIFFERENT ASSUMPTIONS SEVERAL RATE EXPRESSIONS
+.( P.( +./ P./ P/D
R K
+.( P.( +(/ P(/
FOR THE SURFACE REACTION HAVE BEEN PROPOSED )N &IGURE SOME
REACTION RATE EXPRESSIONS ARE DISPLAYED 4HE CONSTANTS A B C AND
,ANGMUIRn(INSHELWOOD
D APPLY TO THE POWER LAW MODEL 4HE RATE CONSTANT IS GIVEN BY K
4HE PARAMETERS +./ +.( AND +(/ ARE THE ADSORPTION CONSTANTS
4HE RATE EXPRESSIONS DEPEND ON THE LOCAL PARTIAL PRESSURES 0./
0.( 0/ AND 0(/ !T GIVEN INLET CONCENTRATIONS THE ./ AND .(
+.( P.( +./ P./ P/D
R K
+./P./ +.( +.(P.( +(/P(/
OUTLET VALUES ARE COMPUTED USING THE REACTOR CONTINUITY EQUATIONS
FOR .( AND ./ 4HE PARAMETERS ARE ADJUSTED SUCH THAT THE SUM OF
&IGURE 3AMPLE OF SELECTED MODELS
"
ALL FUNCTIONS CONTROLLED VIA SIMPLE KEYPAD
EIGHT INDIVIDUAL INJECTORS WITH
INDEPENDANT CONTROL OF TEMPERATURE
PRESSURE REAGENT ADDITION
AND GAS DELIVERY
0ARALLEL EXPERIMENTATION RIG WITH REACTORS
FOR GAS PHASE REACTIONS OVER A FIXED BED
%NDEAVOR UNIT WITH REACTORS FOR GAS LIQUID SLURRY REACTIONS EG HYDROGENATION
&IGURE (IGHnTHROUGHPUT EXPERIMENTATION EQUIPMENT REPRODUCED COURTESY OF A ARGONAUT TECHNOLOGIES B ZETON ALTAMIRA
MOD
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
INETIC
MODELS ! CASE STUDY OF THE SELECTIVE REDUCTION OF ./ BY .(
0ARAMETER ESTIMATION
&OR ALL SELECTED MODELS THE LEAST
SQUARES ESTIMATES OF THE RATE
CONSTANT AND THE ADSORPTION COEFlCIENTS HAVE BEEN lTTED (OWEVER
IN MANY CASES EXTREMELY LARGE STANDARD ERRORS AND MUTUAL
CORRELATIONS OF THE ESTIMATED PARAMETERS WERE EXPERIENCED )N
THE ,ANGMUIRn(INSHELWOOD MODEL THE CORRELATIONS BETWEEN K AND
/
+./ AND BETWEEN +.( AND +(/ WERE AND RESPECTIVELY
4HIS INDICATES ILL
CONDITIONED BEHAVIOR OF THE ESTIMATION PROBLEM
INCLUDING VERY SENSITIVE AND LESS RELIABLE PARAMETER RESULTS
5SING THE hPARAMETER
IN
DENOMINATORv PRINCIPLES THESE INACCURATE
RESULTS HAVE BEEN CONSIDERABLY IMPROVED !FTER DIVISION OF THE
NUMERATOR AND THE DENOMINATOR OF THE ,ANGMUIRn(INSHELWOOD
( /
./.(
RATE BY THE COMMON PARAMETER PRODUCT K +.( +./ AND REARRANGING
THE PARAMETERS IN THE DENOMINATOR NEARLY ALL HIGH CORRELATIONS
AND HIGH STANDARD ERRORS DISAPPEARED 4HIS REPARAMETERIZATION
PRODUCES A @CLOSE
TO
LINEAR MODEL BY CLEARING OFF CONSTANTS IN THE
NUMERATOR OF THE RATE EXPRESSION
&IGURE #ENTRAL COMPOSTE DESIGN
-ODEL SELECTION
SQUARED RESIDUALS 332 THE DIFFERENCES BETWEEN THE MEASURED
)N ORDER TO SELECT THE BEST MODEL A FURTHER MODEL DISCRIMINATION WAS
AND THE COMPUTED ./ AND .( OUTLET VALUES IS MINIMIZED
CARRIED OUT &IGURE DISPLAYS THE REACTION RATES OF FOUR RIVAL MODELS
SEVERAL FORMS OF ,ANGMUIRn(INSHELWOOD INCLUDING A MODEL WITH
%XPERIMENTAL DATA
SURFACE DISSOCIATION CALCULATED WITH A HIGH (/ FRACTION OF
&IGURE DISPLAYS THE LEVELS OF THE INLET CONCENTRATIONS 4HE VALUES
AT THE REACTOR INLET (ARDLY ANY STATISTICALLY SIGNIlCANT DIFFERENCE
HAVE BEEN ARRANGED USING A CENTRAL COMPOSITE DESIGN CONSISTING
IS EXPERIENCED &IGURE DISPLAYS THE RATES COMPUTED WITH THE
OF CORNERS OF THE CUBE LOWHIGH VALUES STAR POINTS ORANGE
SAME PARAMETERS AT A MUCH LOWER (/ CONTENT OF 4HE
OUTSIDE THE CUBE AND ONE OR MORE REPLICATES IN THE CENTER !
DIFFERENCES BETWEEN THE RATE VALUES ARE EVIDENT PARTICULARLY AT
COMPOSITE DESIGN HAS BEEN CHOSEN AS IT IS SUITABLE FOR DETERMINATION
HIGH ./ CONCENTRATIONS !DDING EXPERIMENTS CARRIED OUT AT LOW
OF THE NONLINEAR EFFECTS ARISING FROM THE RATE EXPRESSIONS AND THE
(/ CONCENTRATION INCREASED THE DISCRIMINATIVE POWER BETWEEN THE
SOLUTION OF THE DIFFERENTIAL MASS BALANCES
RELEVANT MODELS IN THE SAME WAY OTHER EXPERIMENTAL CONDITIONS
III 4HERE IS CONSIDERABLE OPPORTUNITY TO IMPROVE THE USER
DEVELOPMENTS IN STATISTICAL SEARCH AND OPTIMIZATION
TECHNIQUES
v -OLECULAR MODELING CAN BE EXPECTED TO CONTRIBUTE MORE
TO USEFUL MECHANISTIC INFORMATION AND TO ESTIMATION
OF INITIAL PARAMETER VALUES 4HIS RELATES TO THE RAPID
DEVELOPMENTS IN THE THEORETICAL CHEMISTRY AND COMPU
TATIONAL TOOLS AS WELL AS TO THE DEVELOPMENT IN ASSOCIATED
COMPUTER HARDWARE 4HE LEADING COMPANIES ARE NOW
TARGETING INCREASED COMPUTATIONAL POWER ON THE DESKTOP
TO FACILITATE THIS
v (IGH THROUGHPUT EXPERIMENTATION HAS LARGELY BEEN
ASSOCIATED WITH COMBINATORIAL CHEMISTRY DISCOVERY
AND SCREENING 4HE POTENTIAL IMPACT OF THE GROSS
PARALLELIZATION OF EXPERIMENTAL EQUIPMENT ON KINETIC
MEASUREMENTS SHOULD NOT HOWEVER BE UNDERESTIMATED ;=
0ARALLEL MICROREACTOR UNITS ARE IN USE IN INDUSTRY AND ARE
NOW BECOMING COMMERCIALLY AVAILABLE &IGURE SHOWS
TWO EXAMPLES OF hOFF THE SHELFv PARALLEL SCREENING UNITS
+INETIC DATA MAY BE MORE RAPIDLY MEASURED BUT THIS
FRIENDLINESS OF SOFTWARE FOR MODELING OF REACTORS FOR THE
REGRESSION OF KINETIC DATA TO RATE EXPRESSIONS AND FOR ITS
APPLICATION TO EXPERIMENTAL DESIGN
4HE MAJORITY OF THE RESPONDENTS STATED THAT THE PROBLEMS
INDICATED SHOULD BE SOLVED BY CO
OPERATION AND THIS OF
COURSE WAS THE IMPETUS THAT LED TO THE FORMATION OF %UROKIN
)NTERMEZZO 4HE ABOVE LIST ESSENTIALLY RELATES TO SIMPLY
IMPROVING THE WAY WE USE THE CURRENT TOOLS AND THEIR
INCREMENTAL DEVELOPMENT 4HE ALTERNATE QUESTION IS WHAT ARE
THE POTENTIAL MAJOR STEP CHANGES THAT ARE GOING TO IMPINGE
ON KINETICS RESEARCH IN THE FUTURE 4AKING THE MEDIUM AND
LONG
TERM PERSPECTIVES AS ONE HERE ARE SOME THOUGHTS AS
TO WHAT THE FUTURE MIGHT BRING OR WHAT WE INVOLVED IN
KINETICS RESEARCH OUGHT TO BE CONSIDERING
v 3OFTWARE TOOLS SIMULATION REGRESSION EXPERIMENTAL
DESIGN WILL BE IMPROVED 4HIS WILL RELATE NOT ONLY
TO IMPROVED USER
FRIENDLINESS AND CALCULATION ROUTINES
LEADING TO REDUCED COMPUTATIONAL TIMES BUT ALSO TO
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
DISPLAYING LARGE DIVERGENCE BETWEEN THE MODELS HAVE BEEN
#ONCLUSION
ADDED TO ALLOW FOR OPTIMAL DISCRIMINATION A FORM OF SEQUENTIAL
5SING STATISTICAL TECHNIQUES OPTIMAL MODEL ANALYSIS AND DESIGN FOR
EXPERIMENTAL DESIGN !S A LAST STEP IN THE ANALYSIS OPTIMAL
THE SELECTIVE CATALYTIC REDUCTION OF ./ BY .( HAS BEEN PERFORMED
PARAMETERS OF THE BEST MODEL HAVE BEEN RElTTED USING ALL THE
3PECIAL ATTENTION HAS BEEN PAID TO THE STATISTICAL DESIGN OF THE
DATA
EXPERIMENTS EFlCIENT REPARAMETERIZATION OF THE MODELS AND THE
DESIGN FOR OPTIMAL MODEL DISCRIMINATION
MODEL
MODEL
MODEL
MODEL
MODEL
MODEL
MODEL
2EACTION RATE
2EACTION RATE
MODEL
P
./
&IGURE 2ATE VALUES AT A (/ CONTENT OF
THEN PUTS THE EMPHASIS ON THE STATISTICAL TOOLS TO SET
THE EXPERIMENTAL DESIGN AND PROCESS THE ACQUIRED DATA
4HE THEORY IS THAT COMBINATORIAL OR SIMILAR DISCOVERY
WILL INCREASE THE NUMBER OF NEW PRODUCTS AND SO THIS
INCREASE IN THE EFlCIENCY OF KINETICS RESEARCH WILL BE
REQUIRED SIMPLY TO KEEP PACE
v .ONSTATIONARY METHODS SUCH AS TEMPERATURE PROGRAMMED
REACTION AND TEMPORAL ANALYSIS OF PRODUCTS ARE CURRENTLY
QUITE WIDELY USED TO OBTAIN MECHANISTIC INFORMATION
BUT AS YET THE OUTPUT IS USED IN A PRIMARILY QUALITATIVE
FASHION AND RELATIVELY LITTLE QUANTITATIVE INFORMATION IS
OBTAINED 5NSTEADY STATE TECHNIQUES HAVE THE BENElT THAT
DATA IS ACQUIRED MUCH MORE RAPIDLY 4HE CHALLENGE IS TO
P
./
&IGURE 2ATE VALUES AT A (/ CONTENT OF
UNDERSTAND HOW DATA MEASURED IN A TRANSIENT CONDITION
CAN BE APPLIED QUANTITATIVELY
4HOSE IN THE %UROKIN CONSORTIUM AND THEIR ACADEMIC
PARTNERS WILL BE ACTIVELY ADDRESSING THESE ISSUES OVER THE NEXT
FEW YEARS 4HE CHALLENGES SHOULD NOT BE UNDERESTIMATED )T
WILL REQUIRE MAJOR EFFORT AND INNOVATION TO ACHIEVE THESE
GOALS
&URTHER READING
4HERE EXIST MANY TEXTBOOKS CONCERNING THE THEORETICAL
BACKGROUND OF REACTION KINETICS
4HE FOLLOWING BOOKS ARE SUITABLE FOR A GENERAL AND
BASIC INTRODUCTION OF CHEMICAL KINETICS HOMOGENEOUS AND
HETEROGENEOUS CATALYSIS AND THE THERMODYNAMICS RELATED
WITH THESE "OUDART ;= "OUDART AND $JEGA -ARIADASSOU ;=
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
'UIDELINES FOR 2EPARAMETERIZATION
v 2EPARAMETERIZE !RRHENIUS EXPRESSIONS ACCORDING TO
v 2EPARAMETERIZE ,((7 TYPE EXPRESSIONS BY REMOVING THE
KINETIC PARAMETERS FROM THE NUMERATOR ACCORDING TO FOR EXAM
%A
%
K K O EXP A
2q4
K K REF EXP
/RIGINAL !RRHENIUS EXPRESSION
2EPARAMETERIZED !RRHENIUS EXPRESSION
2q4
PLE
K+ P + P
R ! ! " "
+ ! P! + "P"
/RIGINAL ,((7 EXPRESSION
7HERE K REACTION RATE COEFFICIENT
K O PRE
EXPONENTIAL FACTOR
%A
K REF K O EXP
2 q 4REF
4
THE REPARAMETERIZED REACTION TEMPERATURE IN +
CALCULATED FROM THE REACTION TEMPERATURE 4 IN + ACCORDING TO
P P
R ! "
P! P"
K + ! + " K + " K+ !
2EPARAMETERIZED ,((7 EXPRESSION
4
4 4 REF
4 REF AN ARBITRARILY CHOSEN REFERENCE TEMPERATURE
WITHIN THE EXPERIMENTAL TEMPERATURE WINDOW
)NSTEAD OF K +A AND +" THE COMBINATIONS K+!+" K+"
AND K+! ARE ESTIMATED WHICH ALSO ENHANCES THE lTTING
PROCEDURE
4HIS REPARAMETERIZATION STRONGLY REDUCES THE INTERDEPENDENCY
BETWEEN ACTIVATION ENERGY AND THE PRE EXPONENTIAL FACTOR WHICH
ENHANCES THE lTTING PROCEDURE %STIMATING THE LOG OF KREF INSTEAD
OF KREF ITSELF MAY FURTHER FACILITATE THE PARAMETER ESTIMATION PROCE
DURE BECAUSE THIS STRONGLY REDUCES THE DIFFERENCE IN UNCERTAINTY
RANGES OF BOTH PARAMETERS
!CKNOWLEDGEMENT 4HE AUTHORS ARE GRATEFUL TO 3JOERD VAN DER 7AL FORMERLY 3HELL 2ESEARCH AND 4ECHNOLOGY #ENTRE !MSTERDAM 4HE .ETHERLANDS FOR SUPPLYING THIS CASE STUDY
&ROMENT AND "ISCHOFF ;= AND +APTEIJN AND -OULIJN ;= 4HESE
BOOKS COVER THE RANGE FROM THE FUNDAMENTALS OF CHEMICAL
KINETICS UP TO MODELING OF REACTORS !N EXTENSIVE AND USEFUL
PAPER CONCERNING THE MODELING OF CATALYTIC KINETICS IS GIVEN
BY &ROMENT AND (OSTEN ;=
3OURCES OF MORE THOROUGH FUNDAMENTAL BACKGROUND OF
KINETICS OF HETEROGENEOUSLY CATALYZED REACTIONS ALSO DElNED
AS MICROKINETICS ARE $UMESIC ET AL ;= :HDANOV;= 6AN
3ANTEN ;= AND 'OLDEN AND -ANION ;= ! FREQUENTLY USED
METHOD FOR MICROKINETIC MODELING IS THE "OND ORDER CON
SERVATIONn-ORSE POTENTIAL APPROACH "/#n-0 APPROACH
SEE 3HUSTOROVICH ; = AND "ELL ;= "ENZIGER;= DESCRIBES
SEVERAL METHODS FOR ESTIMATING REACTION ENERGETICS ON METAL
SURFACES +ANG AND 7EINBERG ;= GIVE AN OVERVIEW OF METHODS
FOR MODELING OF SURFACE RATE PROCESSES %STIMATIONS OF HEATS
OF CHEMISORPTION OF GASES ON METAL SURFACES CAN BE DONE
USING THE GENERAL RULES DElNED BY 4ANAKA AND 4AMARU ;=
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
CURRICULUM VITAE
2OB "ERGER WAS BORN IN
IN %NSCHEDE 4HE .ETHERLANDS (E
GRADUATED IN AT THE 5NIVERSITY
OF 4WENTE IN 0ROCESS %NGINEERING
(E RECEIVED HIS 0H$ DEGREE IN
AT THE SAME UNIVERSITY ON
RESEARCH CONCERNING NICKEL CATALYSTS
FOR INTERNAL REFORMING OF METHANE
IN MOLTEN CARBONATE FUEL CELLS WITH
0ROF *ULIAN 2OSS $URING A lVE YEAR POSTDOCTORAL POSITION
HE INVESTIGATED THE CATALYTIC AND HOMOGENEOUS PARTIAL
OXIDATION OF METHANE TO SYNTHESIS GAS AT %INDHOVEN
5NIVERSITY OF 4ECHNOLOGY WITH 0ROF 'UY -ARIN )N
HE ACCEPTED HIS CURRENT POST DOCTORAL POSITION AT $ELFT
5NIVERSITY OF 4ECHNOLOGY ON THE %UROKIN PROJECT
%UROKIN CO $ELFT 5NIVERSITY OF 4ECHNOLOGY *ULIANALAAN
", $ELFT 4HE .ETHERLANDS E MAIL 2*"ERGER TNWTUDELFTNL
CURRICULUM VITAE
CURRICULUM VITAE
% (UGH 3TITT WAS BORN IN
IN 3TAFFORD %NGLAND (E OBTAINED
HIS DEGREE IN CHEMICAL ENGINEERING
IN AND HIS 0H$ FOR RESEARCH
INTO THE USE OF ELECTRIC lELDS IN LIQUID
EXTRACTION IN BOTH AT THE 5NI
VERSITY OF "RADFORD 5+ (E SPENT
THE NEXT SIX YEARS AS A LECTURER IN
CHEMICAL ENGINEERING AT THE SAME UNIVERSITY TEACHING AND
RESEARCHING IN SEPARATION PROCESSES
3INCE JOINING )#) IN THE EMPHASIS OF (UGHS WORK HAS
MOVED TO CATALYTIC REACTION ENGINEERING )NITIALLY THE FOCUS
WAS )#)S PETROCHEMICAL BUSINESSES INVOLVING INNOVATION IN
REACTORS AND mOW SHEETS FOR NEW PROCESSES AND FOR MODIlCA
TIONS TO EXISTING PLANTS AS WELL AS PROCESS AND REACTOR MODEL
ING
)N (UGH JOINED )#)S CATALYST AND TECHNOLOGY LICENSING
BUSINESS )#) +ATALCO WHICH MERGED WITH OTHER )#) BUSI
NESSES TO FORM 3YNETIX IN (E HAS CONTINUED TO WORK
IN THE EVALUATION DEVELOPMENT AND COMMERCIALIZATION
OF NOVEL REACTORS AND CATALYTIC PROCESSES INITIALLY FOR ENVI
RONMENTAL APPLICATIONS FOCUSING ON TWO AND THREE PHASE
CATALYTIC REACTORS (IS PRESENT ROLE IS TO LEAD THE STRATEGIC
DEVELOPMENT OF REACTOR APPLICATIONS AND SERVICES TECHNOL
OGIES FOR 3YNETIX 4HIS INVOLVES SIGNIlCANT INTERNAL AND
EXTERNAL COLLABORATION EXEMPLIlED BY %UROKIN OF WHICH HE
IS CURRENTLY CHAIRMAN
3YNETIX 0/ "OX "ILLINGHAM #LEVELAND 43 ," 5+ HUGH?STITT
ICICOM
0ROF DR IR 'UY " -ARIN
IS FULL PROFESSOR OF #HEMICAL
%NGINEERING AT THE 5NIVERSITY OF
'ENT "ELGIUM (E RECEIVED HIS
DEGREE FROM THE 5NIVERSITY OF 'ENT
IN WHERE HE ALSO OBTAINED
HIS 0H$ IN !FTER A POST
DOCTORAL STAY IN AT #ATALYTICA
!SSOCIATES AND 3TANFORD 5NIVERSITY
HE OBTAINED TENURE AT THE 5NIVERSITY
OF 'ENT IN (E TOOK A POSITION OF FULL PROFESSOR IN AT
THE %INDHOVEN 5NIVERSITY OF 4ECHNOLOGY 4HE .ETHERLANDS
WHERE HE TAUGHT ABOUT CHEMICAL REACTORS )N HE
RETURNED TO 'ENT AS DIRECTOR OF THE ,ABORATORIUM VOOR
0ETROCHEMISCHE 4ECHNIEK #HEMICAL REACTION ENGINEERING
CATALYSIS IN GENERAL AND REACTION KINETICS IN PARTICULAR ARE
THE MAIN FOCI OF HIS RESEARCH PROGRAM (E HAS CO AUTHORED
MORE THAN PAPERS IN INTERNATIONAL JOURNALS
,ABORATORIUM VOOR 0ETROCHEMISCHE 4ECHNIEK 5NIVERSITEIT 'ENT
+RIJGSLAAN 3 " 'HENT "ELGIUM
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
ACKNOWLEDGEMENT
/NE OF THE AUTHORS 2*" ACKNOWLEDGES THE lNANCIAL
SUPPORT FROM THE ELEVEN COMPANIES IN THE %UROKIN
CONSORTIUM !KZO .OBEL $OW "ENELUX $3- 2ESEARCH
)&0 4%#(.)0 3HELL 2ESEARCH AND 4ECHNOLOGY #ENTRE
34!4/), ,INDE %NI 4ECNOLOGIE 3YNETIX AND %#
#HEM 4ECHNOLOGIES !LL OF THE AUTHORS ARE GRATEFUL TO
THE MEMBERS OF %UROKIN FOR PERMISSION TO PUBLISH THIS
PAPER
CURRICULUM VITAE
&REEK +APTEIJN WAS BORN IN
IN !MSTERDAM 4HE .ETHERLANDS
(E GRADUATED FROM THE 5NIVERSITY
OF !MSTERDAM IN WITH DEGREES
IN CHEMISTRY AND MATHEMATICS (IS
0H$ ON THE METATHESIS OF ALKENES
WAS RECEIVED AT THE SAME UNIVERSITY
!S A POSTDOC HE FOCUSED ON COAL
SCIENCE AND HETEROGENEOUS CATALYSIS
)N HE RECEIVED A TENURE POSITION
AT THE 5NIVERSITY OF !MSTERDAM AND MOVED TO $ELFT
5NIVERSITY OF 4ECHNOLOGY IN 3INCE HE WAS
NOMINATED @PERSONAL PROFESSOR IN $ELFT (E SPENT SEVERAL
PERIODS ABROAD AMONG THEM IN THE GROUP OF 6ILLERMAUX
.ANCY &RANCE %.3)# AND OF 0RINS :RICH 3WITZERLAND
%4( (E IS CO AUTHOR OF MORE THAN PUBLICATIONS
AND A CO PROMOTER OF 0H$ STUDENTS #URRENT INTERESTS
COVER THE APPLICATION OF MONOLITHIC STRUCTURES IN CATALYTIC
CONVERSIONS AND RELATED PROCESSES ADSORPTION AND DIFFUSION IN
ZEOLITES AND ZEOLITIC MEMBRANES AND TRANSIENT KINETICS 4HE
RELATED SPECIlC APPLICATIONS OF HETEROGENEOUS CATALYSIS COVER
SELECTIVE HYDROGENATION AND OXIDATION ./ DECOMPOSITION
&ISCHERn4ROPSCH AND lNE CHEMICALS PRODUCTION
$ELFT 5NIVERSITY OF 4ECHNOLOGY *ULIANALAAN ", $ELFT 4HE .ETHERLANDS
CURRICULUM VITAE
*ACOB ! -OULIJN WAS BORN IN
IN (ARLINGEN 4HE .ETHERLANDS (E
GRADUATED IN AND RECEIVED
HIS 0H$ AT THE 5NIVERSITY OF
!MSTERDAM IN ON THE 3TIMULUS
2ESPONSE TECHNIQUE APPLIED TO PACKED
BEDS (ELD A TENURE POSITION SINCE
AND BECAME PROFESSOR IN
#HEMICAL %NGINEERING IN AT
THE 5NIVERSITY OF !MSTERDAM -OVED
TO $ELFT 5NIVERSITY OF 4ECHNOLOGY IN FOR THE )NDUSTRIAL
#ATALYSIS CHAIR 3PENT A SABBATICAL IN IN $ELAWARE
53! WITH "RUCE 'ATES AND WAS VISITING PROFESSOR AT THE
5NIVERSITY OF 'ENT
(E HAS BEEN #4! FOR THE
5NITED .ATIONS IN #HINA FROM (IS RESEARCH INTERESTS
COVER A WIDE lELD FROM #OAL 3CIENCE TO (ETEROGENEOUS
#ATALYSIS AND %NGINEERING WITH THE EMPHASIS ON THE
APPLICATION OF CATALYSIS IN PRACTICE 4HE USE OF STRUCTURED
CATALYSTS FOR MULTIPHASE OPERATION IS A MAJOR CURRENT RESEARCH
TOPIC 3PECIlC SUBJECTS COVER PETROCHEMICALS CHEMICALS AND
ENVIRONMENT 4HE INTEREST IN CARBON IS STILL LIVING IN THE
RESEARCH ON THE CATALYTIC COMBUSTION OF DIESEL SOOT AND THE
APPLICATION OF CARBON AS A CATALYST SUPPORT (E IS CO
AUTHOR
OF MORE THAN PUBLICATIONS CO
EDITED BOOKS AND WAS
PROMOTOR OF OVER 0H$ STUDENTS
$ELFT 5NIVERSITY OF 4ECHNOLOGY *ULIANALAAN ", $ELFT 4HE .ETHERLANDS
%UROKIN #HEMICAL REACTION KINETICS IN PRACTICE
REFERENCES
;=
!.2 "OS , ,EFFERTS '" -ARIN AND -('- 3TEIJNS +INETIC RESEARCH ON
;= '& &ROMENT AND ,( (OSTEN #ATALYTIC KINETICS MODELLING )N #ATALYSIS SCIENCE
HETEROGENEOUSLY CATALYSED PROCESSES ! QUESTIONNAIRE ON THE STATE OF THE ART IN
INDUSTRY !PPL #ATAL ! 'ENERAL
;=
3URVEY OF GAPS NEEDS AND OPPORTUNITIES IN INDUSTRIAL CATALYSIS .ETWORK ON
"ERLIN PP
;= *! $UMESIC $& 2UDD ,- !PARICIO *% 2EKOSKE AND !! 4REVIRO 4HE MICRO
#ATALYSIS IN %UROPE .)#% CO $%#(%-! &RANKFURT AM -AIN 'ERMANY
KINETICS OF HETEROGENEOUS CATALYSIS !#3 7ASHINGTON $# PP
WEB SITE HTTPWWWDECHEMADEDEUTSCHDECHEMAPAGESFRAMENAVHTM 3EP
;= 60 :HDANOV %LEMENTARY PHYSICOCHEMICAL PROCESSES ON SOLID SURFACES 0LENUM
;=
A . 7AKAO AND 3 +AGUEI (EAT AND MASS TRANSFER IN PACKED BEDS 'ORDON
0RESS .EW 9ORK
;= 2! VAN 3ANTEN AND *7 .IEMANTSVERDRIET #HEMICAL KINETICS AND CATALYSIS
AND "REACH 3CIENCE 0UBLISHERS )NC .EW 9ORK FOR MASS TRANSFER COEF
lCIENTS IN lXED BEDS
0LENUM 0RESS .EW 9ORK
;= $- 'OLDEN AND *! -ANION !PPLICATIONS OF CHEMICAL KINETICS !DVANCES IN
B !0 DE 7ASCH AND '& &ROMENT (EAT TRANSFER IN PACKED BEDS #HEM %NG
3CI FOR HEAT TRANSFER COEFlCIENTS IN lXED BEDS
CHEMICAL KINETICS AND DYNAMICS %D *2 "ARKER 6OL PP
;= % 3HUSTOROVICH 4HE BOND ORDER CONSERVATION APPROACH TO CHEMISORPTION AND
C 62 #HOUDHARY AND ,+ $ORAISWAMY $EVELOPMENT OF CONTINUOUS STIRRED
HETEROGENEOUS CATALYSIS APPLICATIONS AND IMPLICATIONS !DV #ATAL
GAS SOLID REACTORS FOR STUDIES IN KINETICS AND CATALYST EVALUATION )ND %NG #HEM
0ROCESS $ES $EVELOP FOR MASS TRANSFER COEFlCIENTS IN
;= % 3HUSTOROVICH -ECHANISMS AND INTERMEDIATES OF METAL SURFACE REACTIONS BOND
"ERTY TYPE REACTORS
;=
ORDER CONSERVATION VIEWPOINT )N *" -OFFAT 4HEORETICAL ASPECTS OF HETEROGE
A 0( #ALDERBANK -IXING %DS 67 5HL AND *" 'RAY 6OL !CADEMIC
0RESS .EW 9ORK PP FOR GAS LIQUID MASS TRANSFER COEFlCIENTS IN
NEOUS CATALYSIS 6AN .OSTRAND 2EINHOLD .EW 9ORK
;= !4 "ELL 2ELATIONSHIP OF REACTION ENERGETICS TO MECHANISM AND KINETICS OF HET
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