Catalysis Intro 1
Summary of Industrial Catalytic Processes
Process
Typical Catalysts
Petroleum Refining
Cracking
Pt/Re on alumina, Zeolites
Reforming
Pt/Re/Ge/Sn on alumina (dehydrogenation)
Hydrocracking
alumina, zeolites, Pt
Alkylation
Hydrodesulfurization
H2SO4, HF
(Mo-Co) oxides, (Mo-Ni) oxides
Hydrodenitrogenation
(W-Ni) oxides
Chemical Manufacturing
Natural Gas desulfurization
ZnO, Cu, Fe on activated C
Hydrogenations
Raney Ni, Raney Co, Pt, Rh
Ammonia synthesis
promoted Fe
Methanol synthesis
Cu-ZnO
Dehydrogenation
Butadiene: Fe2O3, Pt/Re on alumina
styrene: Zn, Cr, Fe or Mn oxides
Oxidations
ethylene oxide: Ag
nitric acid: Pt/Rh mesh/gauze
sulfuric acid: V2O5
maleic, phthalic anhydrides: V2O5
formaldehyde: Ag or Cu; Mo, Fe, V oxides
Polymerizations
Ziegler-Natta polypropylene: Al alkyls + TiCl3
Dow single site polypropylene: Ti metallocene
Phillips -- Cr oxide on silica
Polyethylene (low density): peroxides, peresters
Polystyrene: benzoyl peroxide
Urethanes: amines, organo-tin, phosphine oxides
Hydroformylation
Union Carbide/Hoechst/BASF: Rh/PPh3
Exxon/BASF: HCo(CO)4
Shell: HCo(CO)4(PR3) (R = bulky alkyl)
Catalysis Intro 2
Catalytic Production of the Top Organic Industrial Chemicals
Ranking
Chemical
#4
Ethylene
#10
Catalyst: Zeolites, Pt/Re on Al2O3 support
Conditions: 850C, 20-50 atm
Propylene
Steam Cracking of Hydrocarbons:
C3H8(g)
C3H6(g) + C2H4(g) + CH4(g) H2(g)
Dichloroethane
15 billion lbs
#16
Steam Cracking of Hydrocarbons:
larger hydrocarbon
smaller hydrocarbon + H2
C2H6(g)
C2H4(g) + H2(g)
33 billion lbs
18 billion lbs
#12
Production
Benzene
10 billion lbs
Catalyst: Zeolites, Pt/Re on Al2O3 support
Conditions: 850C, 20-50 atm
Direct Chlorination:
C2H4(g) + Cl2(g)
Catalyst: FeCl3 or AlCl3
ClCH2CH2Cl(g)
Oxychlorination:
2C2H4(g) + 4HCl(g) + O2
2ClCH2CH2Cl(g) + 2H2O
Catalyst: Cu salts on SiO2 or Al2O3 supports
Hydrocarbon Reforming (dehydrogenation)
C6H14(g)
C6H12(g)
toluene
C6H12(g) + H2(g)
C6H6(g) + 3H2(g)
benzene + methane
Endothermic!
Endothermic!
Catalyst: Pt/Re/Ge/Sn on Al2O3 support
#17
Ethyl Benzene
C6H6(g) + C2H4(g)
C6H5C2H5
1. Catalyst: Liquid phase system with AlCl3
9 billion lbs
2. Catalyst: Zelolite Lewis Acid based gas phase process
Classic Friedel-Crafts rxn.
#19
Vinyl Chloride
8 billion lbs
#20
Styrene
ClCH2CH2Cl(g)
H2C=CHCl(g) + HCl(g)
This reaction is often coupled with the oxychlorination reaction
to produce dichloroethane, this allows recycling of the HCl.
Dehydrogenation of ethyl benzene
Catalyst: Fe oxides on Al2O3 support
8 billion lbs
#21
Conditions: 550-600C
Terephthalic Acid Amoco Process:
p-CH3-C6H4-CH3 + 3O2
8 billion lbs
p-HOOC-C6H4-COOH + H2O
Catalyst: Co/Mn salts (with some heavy metal bromides)
Conditions: liquid acetic acid solution, 200C, 20 atm
Ti or Hastelloy C lined reactor (very corrosive)
Catalysis Intro 3
#22
Methanol
CO + H2
CH3OH
Catalyst: ZnO/Cu salt
7 billion lbs
#24
Ethylene Oxide
Conditions: > 100 atm, 200-300C
C2H4(g) + O2
ethylene oxide
Catalyst: Ag
#26
6 billion lbs
Conditions: 300C
Toluene
Catalytic Reforming of methyl cyclohexane and derivatives
Catalyst: Pt/Re on Al2O3 support
#27
6 billion lbs
Conditions: 500C and 25 atm
Xylenes
Catalytic Reforming of 1,4-dimethylcyclohexane
Catalyst: Pt/Re on Al2O3 support
#28
5.5 billion lbs
Conditions: 500C and 25 atm
Ethylene Glycol
ethylene oxide + H2O
5 billion lbs
#29
Butylaldehyde
HOCH2CH2OH
Catalyst: H2SO4 (0.5 - 1%), 50-70C
Conditions: Thermal @ 195C and 15 atm.
Hydroformylation -- Union Carbide/Celanese/BASF
propylene + H2 + CO
5 billion lbs
CH3CH2CH2CHO
Catalyst: homogeneous Rh/PPh3 catalyst
Conditions: 100-125C, 8-25 atm
#31
Cummene
3.7 billion lbs
benzene + propene
C6H5CH(CH3)2
1. Liquid phase catalysts: H2SO4, AlCl3, HF
2. Gas phase catalyst: H3PO4 on SiO2
Friedel Crafts reaction
Conditions: 35-40C, 7 bar (liquid); 200-300C, 20-40 bar (gas)
Cumene is mainly used to produce phenol and acetone.
#32
Acetic Acid
3.5 billion lbs
CH3OH + CO
CH3COOH
Catalyst: homogeneous RhI2(CO)2
(Monsanto Acetic Acid process)
Conditions: 150C, 35 atm
Catalysis Intro 4
Homogeneous Catalysis
[catalyst]
A + B
Remember that thermodynamics and equilibrium still rule!! A catalyst
only speeds up the rate at which a chemical reaction reaches
equilibrium. The actual equilibrium constant (thermodynamics) is NOT
affected by the catalyst. Therefore, non-spontaneous reactions are
usually NOT suitable for catalytic applications.
Advantages/Disadvantages of Homogeneous Catalysts Relative to
Heterogeneous Catalysts
Good homogeneous catalysts are:
good
generally far more selective for a single product
far more active
far more easily studied from chemical & mechanistic aspects
far more easily modified for optimizing selectivity
bad
far more sensitive to permanent deactivation
far more difficult for acheiving product/catalyst separations
Heterogeneous catalysts dominate chemical and petrochemical industry: ~ 95% of all chemical processes use
heterogenous catalysts.
Homogenous catalysts are used when selectivity is critical
and product-catalyst separation problems can be solved.
Catalysis Intro 5
Homogeneous or Heterogeneous?
Because many homogeneous catalysts decompose to form
heterogeneous catalysts, and some heterogeneous catalysts can dissolve
to form homogeneous catalysts, one should always be careful about
making assumptions on what type of catalyst one is using in any new
catalytic experiment. There are several general ways to test whether a
catalyst is homogeneous or heterogeneous.
1) Exposure to elemental Hg will generally poison a heterogeneous
catalyst
2) Exposure to polythiols will poison most homogeneous catalysts
3) Light scattering studies to identify the presence of colloids
(heterogeneous)
4) Product selectivity studies
e.g., polymer bound alkenes:
Catalyst
+ H2
Polymer
Polymer
Catalyst
Homo/Hetero
% Yield
RhCl(PPh3)3
Ni(OAc)2 + NaBH4
[Rh(nbd)(PR3)2]+
Pd/C
[Ir(cod){P(i-pr)3}(py)]+
homo
hetero
homo
hetero
homo
100
-90
-100
Catalysis Intro 6
Some Catalysis Terminology
Turnover (TO) -- one loop through the catalyst cycle. Typically one
equivalent of reactant is converted to one equivalent of product (per
equivalent of catalyst).
Turnover Frequency (TOF) or Turnover Rate -- the number of passes
through the catalytic cycle per unit time (typically sec, min or hrs). This
number is usually determined by taking the # of moles of product
produced, dividing that by the # of moles of catalyst used in the
reaction, then dividing that by the time to produce the given amount of
product. The units, therefore, are usually just time1. Note that the rate
of a batch catalytic reaction is fastest at the very beginning of when the
reactant concentration is the highest and generally slows down as the
reaction proceeds -- stopping when all the reactant is used up. Note the
graph below for the production of aldehyde product from the
homogeneously catalyzed reaction of vinyl acetate, H2, and CO.
Vinyl Acetate Hydroformylation
sampling from
autoclave causes
pressure glitches
0.3mM catalyst -- 85C/90 psi H 2/CO
2,000
1,800
4.5
Uptake curve
1,600
4
1,400
Equiv
Aldehyde
3.5
-1
1,200
kobs = 0.0076 min
1,000
Ln plot
Prod
800
Ln P)
2.5
600
Initial TOF
8 TO/min
476 TO/hr
400
2
1.5
200
0
0
10
15
20
Time (hours)
The TOF, therefore, will vary throughout the course of a batch reaction.
The Initial TOF is defined as the initial part of a catalytic reaction
where the rate is the fastest and essentially linear. A far better measure
Catalysis Intro 7
of rate is the observed rate constant kobs, which allows one to reproduce
the entire product production curve given a set of reactant & catalyst
concentrations. In the above graph, the reaction is pseudo-first order in
excess reactant alkene (vinyl acetate concentration ~ 0.6 M, catalyst 0.3
mM) and kobs is determined from a ln plot of the change in H2/CO
pressure (reactant concentration) versus time for this rxn. When
reporting kobs chemists often normalize it to a certain catalyst
concentration (1 mM, for example).
Turnover Number (TON) -- the absolute number of passes through the
catalytic cycle before the catalyst becomes deactivated. Academic
chemists sometimes report only the turnover number when the catalyst
is very slow (they dont want to be embarassed by reporting a very low
TOF), or decomposes quite rapidly. Industrial chemists are interested in
both TON and TOF. A large TON (e.g., 106 - 1010) indicates a stable,
very long-lived catalyst. TON is defined as the amount of reactant
(moles) divided by the amount of catalyst (moles) times the % yield of
product. Authors often report mole % of catalyst used. This refers to
the amount of catalyst relative to the amount of reactant present. 10
mole % = 10 TO, 1 mole % = 100 TON, 0.01% = 10,000 TON.
ee (enantioselectivity) this defines the enantioselectivity of an
asymmetric catalyst that produces more of one optically active
enantiomer (R enantiomer, for example) than the other (S enantiomer).
ee is defined as:
ee
RS
RS
100%
A catalyst that makes an equal amount of R and S enantiomers has 0%
ee (a racemic mixture). 85% or higher is generally considered a good
ee, although that depends on what the best known catalyst can do
relative to that being reported.
Catalysis Intro 8
Catalysis Data in Publications
There is a lot of mediocre/bad catalysis reported all the time in
chemistry publications. One often has to dig into the data to figure this
out. The things one wants to typically look for to tell whether there is
good catalysis or not include:
1) # of turnovers performed more is better
2) TOF (turnover frequency) faster is better
3) Good selectivity for the product this includes chemoselectivity,
regioselectivity, and enantioselectivity (if applicable)
4) Reaction conditions harsh? Mild? Unusual? Concentrations?
To figure out the number of turnovers you need to know the amount of
substrate (reactant) and catalyst:
Turnovers
# moles (equivalents) reactant (substrate)
# moles (equivalents) catalyst
But authors often list these values in different ways and you may have
to do some interpreting. The most common alternate way of
representing the substrate:catalyst ratio is mole %. This is especially
common for organic chemists doing Pd-catalyzed coupling reactions.
10 mole % catalyst means that there is 10% as much catalyst as
substrate on a molar basis. This is equivalent to 10 turnovers.
10 mole % catalyst = 10 turnovers
5 mole % catalyst = 20 turnovers
1 mole % catalyst = 100 turnovers
0.1 mole % catalyst = 1000 turnovers
0.01 mole % catalyst = 10,000 turnovers
These represent the
theoretical maximum #
of turnovers. One also
has to note the % yield
or the % conversion of
substrate into product to
figure out the actual # of
turnovers!!
Catalysis Intro 9
Example: Consider the following catalytic data reported in a J. Am.
Chem. Soc. communication (very prestigious) a number of years ago:
O
R + CO + H2O
HO
Hydrocarboxylation
Lets look at the last line of data from the table since that had the
highest ee. The third column contains the important information about
the ratio of reactant (often referred to as substrate), chiral chelating
ligand L*, and PdCl2.
The authors had 7.7 equivalents of reactant, 0.38 equivalents of chiral
ligand, and 1 equivalent of Pd. This means that the maximum number
of turnovers they could do is defined by the amount of reactant (moles
or equivalents) divided by the amount of catalyst (moles or equivalents).
max turnovers
equivalents reactant 7.7
7.7
equivalents catalyst 1.0
Catalysis Intro 10
7.7 turnovers is small and not at all impressive. Hydrocarboxylation,
however, is a difficult catalytic reaction and doing it asymmetrically is
even more impressive.
Of course, 7.7 turnovers assumes 100% yield, which they did not get.
The actual number of turnovers needs to be reduced by the % yield,
which they report as 64%, so the actual number of turnovers is:
actual turnovers 7.7 0.64 4.9
4.9 turnovers is barely catalytic. What about the TOF? Well you have
to read a little footnote to find how long they ran the reaction to get their
64% yield: 18 hours at 1 atm of CO. The TOF is the number of
turnovers divided by the time:
TOF
4.9 turnovers
0.27hr 1
18 hr
Well, 0.27 turnovers/hr is also barely catalytic. But that 91% ee is quite
impressive isnt it. Or is it?
The authors only added 0.38 equivalents of chiral ligand to 1 eq of
PdCl2 to generate, at most, 0.38 equivalents of chiral catalyst (assuming
one ligand per Pd). This is rather unusual, since one usually adds a little
excess of chiral ligand to generate a chiral catalyst, even when dealing
with a chelating ligand. There are examples where one can add less
ligand than metal complex due to the fact that the metal-ligand catalyst
generated is much more active than the starting metal complex itself.
But one almost always adds enough ligand (or extra since the ligand can
dissociate) to generate as much of the presumed catalytically active
species as possible.
Catalysis Intro 11
The ligand that the author is using is:
O
O
OH
P
O
BNPPA
This is being used under rather acidic conditions (typically needed for
Pd-catalyzed hydrocarboxylation) and under these conditions it is highly
unlikely that it would be able to function as a ligand. Remember that
the late transition metals dont particularly like oxygen donor ligands
(weaker bonding).
This fact makes the high ees rather suspect. And a number of research
groups (Hoechst Celanese, Union Carbide, etc.) have found (although
not published) that the actual ee for this catalyst is close to 0.
So it is often important to read the experimental conditions very
carefully and with a critical eye.
Catalysis Intro 12
Problem: Consider the following catalytic data reported in a recent
publication. What information is missing?
Catalysis Intro 13
Problem: Beller and coworkers have reported (Angew. Chem., 2001, 40,
3408-3411) on hydroformylation catalysis using HRh(CO)(Naphos).
The table of catalytic data from their paper is shown below. For
experiment # 1, how many turnovers did the authors do? Clearly show
how you calculate your number. Is there any important data missing
from this table?
Catalysis Intro 14
Problem: What information is missing from the following Table of
catalytic results (they defined the ligands used elsewhere in the paper).
How many turnovers are they doing?
