Beruflich Dokumente
Kultur Dokumente
A literature study of
New Hydroformylation Techniques
Date: 08 – 01 – 06
Pages: 30
Appendices: 2
The report is created for the Process Development group. The subject is provided and
accompanied by L.J.P. v/d Broeke. I would like to thank him and anybody else of the
Process Development group who advised me doing my research for this report.
2
Summary
The subject of this report is hydroformylation reactions. In a hydroformylation reaction
linear and branched aldehydes are formed out of alkenes (olefins) and syngas. There are
two kind of basic processes in the industry that are used for hydroformylation reactions.
Homogeneous processes, where cobalt and rhodium catalysts are used and a biphasic
process where rhodium is used as catalyst. The rhodium catalyst is modified by ligands to
form an active catalyst complex; phospine ligands used in industry are
triphenylphosphine oxide (TPPO) for homogeneous systems and meta-trisulfonated
triphenylphosphine (TPPTS) for biphasic systems.
The current industrial processes have limitations; the most important are mentioned here.
In case of the homogeneously processes, separation of the product mixture and the
catalyst complex is difficult because the mixture is in the same phase. Separation of long
chain olefins is even more difficult because distillation at high temperatures causes
degradation of the catalyst.
It is also hard to get high conversions and control selectivity’s of the products (linear
aldehydes is mostly the desired product). Especially conversion of higher olefins in
biphasic systems is difficult because of the low solubility in the aqueous phase.
Another problem is that organic solvents, used in hydroformylation, are environmental
unfriendly. Other solvent are therefore preferred.
At the end three techniques that are less well-known are described. These techniques are
hydroformylation under high pressure, with a ruthenium catalyst and with a sulfonated
xantphos ligand. The first two are not that likely to be used in commercial industry.
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Table of contents
PREFACE ..................................................................................................................................................... 2
SUMMARY................................................................................................................................................... 3
1. INTRODUCTION .............................................................................................................................. 5
2. HYDROFORMYLATION IN GENERAL....................................................................................... 6
2.1 HYDROFORMYLATION REACTION ................................................................................................. 6
2.2 PRODUCTS AND MARKETS ........................................................................................................... 7
3. COMMERCIALLY APPLIED PROCESSES ................................................................................. 8
3.1 COBALT BASED CATALYST ........................................................................................................... 8
3.1.1 BASF process.......................................................................................................................... 8
3.1.2 Exxon process ......................................................................................................................... 8
3.1.3 Shell process ........................................................................................................................... 9
3.2 RHODIUM-BASED PROCESSES ....................................................................................................... 9
3.2.1 UCC process........................................................................................................................... 9
3.2.2 Ruhrchemie/Rhône-Poulenc process .................................................................................... 10
4. NEW TECHNIQUES AND RESEARCH AREAS ........................................................................ 11
4.1 INTRODUCTION........................................................................................................................... 11
4.2 HYDROFORMYLATION IN SUPERCRITICAL CARBON DIOXIDE (SCCO2) ........................................ 11
4.2.1 General experimental setup.................................................................................................. 12
4.2.2 Results................................................................................................................................... 12
4.2.3 Hydrofromylation in scCO2 using a polymer based catalyst ................................................ 14
4.3 MICELLAR SYSTEMS ................................................................................................................... 16
4.3.1 Experimental setup ............................................................................................................... 16
4.3.2 Results................................................................................................................................... 16
4.4 SUPPORTED RHODIUM COMPLEXES ON SILICA NANOPARTICLES ................................................. 19
4.4.1 Experimental setup ............................................................................................................... 19
4.4.2 Results................................................................................................................................... 19
4.4.3. Silica-immobilized catalyst in scCO2 .................................................................................... 21
4.5 POLYETHER PHOSHITE AS LIGAND .............................................................................................. 22
4.5.1 Experimental setup ............................................................................................................... 22
4.5.2 Results................................................................................................................................... 22
4.5.3 OPGPP in combination with ruthenium catalyst.................................................................. 24
4.6 REMAINING TECHNIQUES ........................................................................................................... 25
4.6.1 Ruthenium catalyst ............................................................................................................... 25
4.6.2 High-pressure hydroformylation .......................................................................................... 25
4.6.3 Sulfonated Xantphos ligand.................................................................................................. 25
5. DISCUSSION .................................................................................................................................... 27
5.1 HYDROFORMYLATION IN SCCO2 ................................................................................................ 27
5.2 MICELLAR SYSTEMS ................................................................................................................... 27
5.3 SILICA SUPPORTED CATALYST .................................................................................................... 28
5.4 POLYETHER PHOSPITE AS LIGAND .............................................................................................. 28
5.5 REMAINING TECHNIQUES ........................................................................................................... 28
REFERENCE LIST ................................................................................................................................... 30
APPENDIX I: PROCESS FLOW DIAGRAMS OF INDUSTRIAL PROCESSES ..................... 31
APPENDIX II: RHODIUM CATALYST CYCLE ........................................................................... 34
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1. Introduction
The subject of this term paper is to study new techniques of hydroformylation reactions.
The goal is to project an overview of new (catalytic) processes and developments of these
types of reactions.
Hydroformylation is a reaction where olefins react with synthesis gas (CO and H2) in
presence of homogeneous catalysts to form linear and/or branched aldehydes. This
homogeneous catalyst process is one of the few applied on commercial and industrial
scale.
There is a big market for linear aldehydes and there are several problems in the industrial
applied processes. The most important problems are:
The use of organic solvents to dissolve the catalyst, organic solvents cause environmental
pollution and are toxic.
The reactant, products and catalyst are in the same phase, the catalyst must be recovered
and separated from the product after the reaction, which is difficult and is energy
consuming because the mixture is in the same phase.
Recovery of the catalyst is very important because it is an expensive metal complex bases
on rhodium, cobalt and sometimes platinum. There is also loss in activity and degradation
of the catalyst when they are used multiple times in the reaction process.
In the current processes is it hard to get high conversions and control selectivity’s of the
products, because both linear and branched aldehydes are formed, mostly the linear form
is desired. Especially conversion of higher olefins is difficult.
There is also very little knowledge of the kinetics of the reaction.
In order to improve the industrial processes and overcome the biggest problems
mentioned above, there is a lot of research and development on hydroformylation
reactions.
The report contains the following subjects. In chapter 2 a brief description of general
themes, such as the hydroformylation reaction and markets for the products is given.
In chapter 3 the most important existing industrial processes will be discussed, with their
performances and limitations.
In the 4th chapter the recent developments in hydroformylation reactions will be
introduced and discussed, by means of explanations of experiments. In chapter 5, the
final chapter, the described techniques will be compared with the existing industrial
processes and an opinion is given, whether these newly developed techniques can or will
be scaled up to commercially achievable processes or remain laboratory research.
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2. Hydroformylation in general
In this chapter first the reaction mechanism will be described firstly and an overview of
the products will be given.
During the homogeneous catalysis the catalyst is dissolved (often modified with ligands)
in a suitable organic solution. Another possibility is a biphasic system where the catalyst
is dissolved in one phase (aqueous) and the reactants in another phase (organic). More
details of these processes will be reported in the chapter ‘Commercially applied
processes’.
Catalysts that are used for industrial hydroformylation processes are cobalt and rhodium
based metal complexes. Also ruthenium and platinum are used as catalyst, but not for
industrial applications, they have much lower activity. Typical complexes are HCo(CO)4,
HCo(CO)3, HCo(CO)3PBu3 and HRh(CO)(PR3)3. The catalysts complexes are modified
by ligands.
The processes with cobalt and rhodium catalyst use phosphines as electron-donating
ligand. In the biphasic system a water soluble phosphine is used as a ligand, transferring
the reaction into the aqueous phase. The only classes of ligands used in industrial
hydroformylation are phosphines PR3 (R = C6H5, n-C4H9), triphenylphosphine oxide
(TPPO), meta-trisulfonated triphenylphosphine (TPPTS) and in some experimental cases
phospites P(OR)3.
The modified catalyst complexes are i.e. HRh(CO)2(TPP)2, HRh(CO)2(TPPTS)3, etc.
Many of these complexes are in equilibrium with each other in a complex catalytic cycle.
The different complexes cause different product, i.e. HRh(CO)(TPP)2 causes linear
aldehydes and HRh(CO)2TPP causes branched products. These complexes are formed out
of the key intermediate HRh(CO)2(TPP)2 as in figure 2.2 which is a part of the Wilkinson
hydroformylation cycle for modified rhodium catalysts (dissociative and associative
mechanisms, ref 10).
6
Figure 2.2: Initial equilibria forming the active catalyst species; L=TPP
The main product is butanal with a share of 73%. The formed aldehydes are used in the
bulk and specialty chemical business. They can be used to form other compounds like
amines, alcohols, carboxylic acids and ethers for instance. Main consuming industries of
aldehydes are the polymer- (especially PVC) and detergent industry.
The most desired products are in the linear form, but some products are desired in the
branched i.e. hydroformylation of styrene into a branched aldehyde is especially
important because it is a main step in ibuprofen production.
7
3. Commercially applied processes
There are three main types of commercially applied processes, the cobalt based catalyst,
the rhodium bases catalyst and the biphasic homogeneous hydroformylation.
Gas-phase hydroformylation with heterogeneous catalysts plays no role today.
Some of the important industrial processes will be discussed shortly in this paragraph.
The most important parameters will be shown. The process flow diagrams of the
described processes are added in appendix I.
The benefit of the Exxon process is that the catalyst does not undergo decomposition and
enters the reactor in its most active/effective form. A big disadvantage is that catalyst
separation and recovery must be carried out under CO pressure to preserve the catalyst.
8
3.1.3 Shell process
In the Shell process reactants in range of C7 – C14 are converted using a phosphine-
modified cobalt catalyst. In this process the product mixture is distillated, the organic
products leave the distillation column at the top and the catalyst is recovered at the
bottom. Before re-entering the reactor the catalyst recycle is upgraded with catalyst and
phosphine ligand. The benefits of this process are the high n/i ratio, the low pressure and
the direct formation of alcohols. The disadvantage is the low activity of the ligand-
modified catalyst, which requires a large reactor volume.
9
dissolved gas, aldehydes, rhodium-phospine complex, free phosphine ligand and the
higher-boiling aldehyde condensation products. The product mixture enters a separator
and a flash evaporator, where the major part of inerts and unconverted reactants is taken
overhead. The flashed-off gases are returned to the reactor. The liquid stream is heated
and is fed to two distillation columns in series. The gaseous aldehydes are sent over the
top and will be condensed and separated from the CO/H2 gas, which is recycled. At the
bottom the catalyst solution is separated and recycled in the reactor. If the feed of the
process has a sufficient purity the catalyst may last more than a year. The BASF and
Mitsubishi rhodium based processes are quite parallel to the UCC process and are
therefore not further discussed.
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4. New techniques and research areas
4.1 Introduction
In this chapter some of the main scientific researches on hydroformylation reactions are
described. Three different kinds of research topics for hydroformylation can be pointed
out. In the first group, studies dealing with the properties of the solutions (used to run the
reaction) are described. In the second and third group research to different catalyst
complexes and ligands are described.
Current industrial processes have reached high standards of performance but uses
traditional techniques, researchers try to find novel techniques which leads to more
sustainable processes. The most important reasons to do research on hydroformylation
reaction are already pointed out in the previous chapters, but they will be mentioned
again for the complete overview.
The current solutions used in the industrial processes are organic solutions, which cause
environmental pollution. Therefore scientists try to find different solutions; preferable
non organic solutions i.e. super critical CO2. Also organic solutions are still studied trying
to improve reaction rates, selectivity and the hydroformylation of higher olefins.
A very important problem is the recovery of the catalyst. The rhodium and cobalt
catalysts are very expensive, so it is very important to maintain the catalyst. The current
processes can recover the catalyst, but several separation units (mostly distillation) are
needed which have limitations and are energy consuming. Research of new catalyst,
ligands and solution and/or new kind of processes is done to have better and easier
catalyst recovery.
The hydroformylation of higher olefins is more difficult then propene for instance. In the
current processes the higher olefin hydroformylation have limitations. In case of the
biphasic process, the heavier olefins have less solubility in the aqueous catalyst phase,
which cause a dramatically drop of reaction rate. Mostly hydroformylation of higher
olefins is carried out in a single organic phase. The catalyst is separated by distillation,
which may result in catalyst decomposition, because of high boiling points of the heavier
products. Therefore much research is done to improve reactions of the higher olefins.
In this chapter new solutions for hydroformylation are discussed. The research subjects
described are: super critical carbondioxide, micellar systems
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First a description is given of the hydroformylation of propylene in scCO2 using a cobalt
catalyst (ref 3). The general setup of the experiment is explained in the next paragraph
and in figure 4.1.
4.2.2 Results
Some important experimental results are shown in this paragraph. The pressure and
temperature are important parameters of the reaction and influence the conversion. In
figure 4.2 the conversion is shown as a function of reaction time at constant temperature
of 88 oC with different pressures. 1 g/batch of catalyst was used, in 282 mL reactor
volume. The result is an increase of the conversion with increasing pressure at a given
reaction time. This increase in conversion levels off at about 2100 psig (144.8 bar).
In the experiments of figure 4.3 the opposite is done, by changing the temperature at
constant pressure of 2400 psig. The result is an increase of the conversion by increasing
the temperature.
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Figure 4.2: Propylene conversion at different Figure 4.3: Propylene conversion at different
pressures, T= 88 oC. temperatures, P= 2400 psig
Table 4.1: Reaction selectivity at different pressures and temperatures with 1.0 g of catalyst/batch (ref. 3)
Pressure Temperature L/B ratio
o
Psig C
2400 78 4.2
2400 88 4.1
2400 98 3.1
2400 108 2.7
1350 88 2.7
1650 88 3.0
2100 88 4.2
2700 88 4.3
During the experiments a possible reaction rate constant is found out of proposed kinetics
from the literature (ref. 3). There is a pseudo-first order rate constant observed, the rate
constant at a constant temperature is a function of hydrogen- and carbon mono-oxide
pressure and the present catalyst. A proposed empirical reaction rate equation is:
PH
r = K ⋅Cp K = kWcat 2
PCO
Where Cp is the concentration of propylene and k is the reaction rate constant, which
depends on pressure. In literature different kind of kinetic models are used to describe
reaction rates, see ref. 4 for another example.
Reaction rate and selectivity can be changed by tuning the pressure and temperature, but
theoretical explanations of the observed results are not given.
There is also another problem. There is still no solution presented to separate the product
and recover the catalyst. In paragraph 4.2.3 and 4.4.3 possible solutions are described.
4.2.3 Hydrofromylation in scCO2 using a polymer based catalyst
In the previous paragraphs it is proven that hydroformylation in scCO2 works. Still there
is now convenient solution to separate the catalyst from the product mixture.
A new approach of catalyst recovery in scCO2 systems is the use of a polymer based
catalyst. In this case the catalyst complex is chemically bound to a polymer. This polymer
based complex is easy to separate by a membrane because of its large size compared to
the products and remaining reactants.
The case discussed in this paragraph is the hydroformylation of styrene into a branched
aldehyde, with a polymer supported rhodium catalyst (ref. 5) This process is a main step
in the production of ibuprofen.
Figure 4.4: catalyst structure Figure 4.5: Formation of the catalytic active
species for the hydroformylation of olefins.
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During the reaction several reactions have to occur before a catalytic cycle starts and the
key intermediate HRh(CO)2L2 (fig. 2.2) is formed. The overall process is given in figure
4.5. It is proposed that the reaction mainly takes place through the dissociative reaction
mechanism, see appendix II.
4.2.3.2 Results
The experimental setup to perform the reaction is comparable with figure 4.1 only a
membrane is placed behind the reactor, to separate the catalyst.
The experiments are reproducible and have a conversion of about 90%, with high
selectivity to branched aldehydes as shown in figure 4.6. In rhodium catalyzed
hydroformylation of styrene, selectivity to branched aldehyde increases as the
temperature decreases. This is due to the stability of the benzylic rhodium species. The
selectivity to branched aldehyde was about 85% at 348 K and nearly 100% at 323 K, both
at 241 bar. An increase of pressure also induces an increase of branched aldehyds with
constant temperature. In most of the used reaction conditions (T: 323 – 348 K, P: 172 –
241 bar) the catalyst was totally soluble, TAN13 more than TAN7.
At total overview of the reaction studies is summarized in table 4.2.
Figure 4.6: styrene hydroformylation reproducibility at 348 K and 172 bar using Rh(TAN13DPPA)3Cl
catalyst.
Hydroformylation of linear olefins with polymer based catalyst are also studied with
good results. Conversions are up to 100% and there is no activity decrease and rhodium
leaching. For further details see ref 6, this is not further described in this report.
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4.3 Micellar systems
Hydroformylation in a biphasic system is already used on industrial scale. Still a lot of
research and development is performed on biphasic systems, one of those developed
techniques are micellar systems. The technique consists in adding appropriate
amphiphilic agent (surfactant or detergent) to a biphasic liquid system. The aqueous and
organic phases form a single stable micellar medium (micro emulsion) with a continues
and dispersed phase. The amphiphilic molecules have a hydrophobic carbon chain and a
hydrophilic head group. Using an amphiphilic ligand it is possible to dissolve organic
molecules into water by creating micelles. The technique is based on transfer of organic
groups into the aqueous phase or to the interface where the catalyst is present.
This has two major advantages; firstly, micelles can dissolve molecules which are
normally not soluble in the bulk solvent. Secondly, there is an enormous interface
between continuous and dispersed phase due to the very small size of micelles (10 – 100
nm). On the other hand there is also a problem, because the stable micellar phase must be
separated into two phases at the end of the reaction, in order to recover the aqueous
catalytic phase.
The experimental results of rhodium based hydroformylation of 1-dodecene with TPPTS
as ligand (ref. 7) are described.
4.3.2 Results
The experimental results are described in this paragraph, three kinds of experiments can
be performed; the first with the different surfactants, the second with alcoholic solvents
instead of surfactants and the third without any additives. The results are listed in table
4.3. Hydroformylation did not occur in absence of surfactant or alcoholic solvent.
The addition of cationic surfactants or alcohol improved the reaction rate of 1-dodecene.
Non-ionic surfactants did not enhance the reaction rate very obvious; this is in contrast of
some other reports in literature. Anionic surfactants inhibit the reaction.
The increase of the reaction rate by adding alcohols is probably caused by changes in
solubility. The solubility of olefins in the aqueous phase or of the catalyst complex in the
organic phase is than increased. A disadvantages effect is that a part of the catalyst can
not be recovered, when it leached into the organic phase.
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Increase in reaction rate by addition of cationic surfactants can be described by two
factors. The first one is the formation of micelles, which cause an increase of the
interfacial area between the phases and it brakes the phase barriers. The second reason is
that the cationic ends of the micelle are orientated to the aqueous phase; this forms a
positive charged ion layer. This layer attracts the anionic active rhodium/TPPTS
complex, HRh(CO)[P(m-C6H4SO3)3]33n- (figure 4.7). This means that the catalyst is
highly concentrated at the interface and more easily coordinated with the olefins in the
micelle. Other experiments are therefore performed with cationic surfactant CTAB,
which is pretty common in other researches (ref 10 i.e.).
Micelles are formed in addition of anionic and non-ionic surfactants, causing increase of
interfacial area, only no high reaction rates were established. In case of non-ionic
surfactant the catalyst concentration at the interface does not increase. In case of the
anionic surfactant the negative charged ion layer of the micelle could not contact with the
negative charged catalytic active species as result of the static repulsion. This causes a
very low catalytic concentration in the interfacial layer.
Table 4.3: Biphasic hydroformylation of 1-dodecene with different surfactants and alcoholic solvents.
Additive Nil. Tween Span SDS CTAB DTAB BDAC Diglycol ethanol propanol
20 40 methylether
Yield (%)1 0 3.8 3 0 61.3 60.9 44.8 12 24.5 42.3
n/i ratio - - - - 6.1 5.6 6.3 3.9 3.4 3.6
Reaction conditions: Rh =6.4x10-4 mol/l, TPPTS/Rh =16, 1-dodecene: 22.6 mmol, heptane: 5 ml, water 20 ml,
surfactant: 5.5x10-3 mol/l, T=100oC, P=0.5MPa, reaction time 120 min. (with alcohols 10 ml of water)
1
conversion of olefin to aldehydes
CTAB: cetyltrimethylammonium brom., DTAB: dodecyltrimethylamm. brom., BDAV: benzyltetradecyldimethylamm. Chloride.
Tween20: polyoxyethylene(20) sorbitan monolaurate, Span40: sorbitan monopalmitate, SDS: sodium dodecyl sulfate.
Figure 4.7: sketch map of catalytic active species in the interfacial layer of cationic micelle
The addition of cationic surfactants is also favourable for linear aldehydes. The micelle
structure creates an orderly and compact micro environment where olefins are solubilized
and coordinated with catalyst complexes, favourable for linear aldehydes. This
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hypothesis is controlled with the following explanation. The stirring rate is changed,
because this would cause variation in the reaction micro circumstances, which could
influence the reaction rate and selectivity. Vigorous stirring will disturb the meta-stable
micelle structure. This hypothesis is confirmed in an experiment, see table 4.4. The rate
constant k of the reaction increases with increasing stirring rate, the selectivity however
decreases. Higher stirring rate is better for the transfer of substrates to the interface, but is
a disadvantage for the formation of micelles.
: conversion
: n/i
The surface tension of the reaction mixture is also measured; at a CTAB concentration of
about 0.6x10-3 mol/l a major decrease in surface tension is measured. This corresponds
with the critical micelle concentration (CMC) and explains the increase in conversion as
seen in figure 4.8.
An important issue of this system is that afterwards organic product phase and aqueous
catalyst phase must be separated. Thus the emulsification of the micellar phase must be
reversible. In the research of micellar hydroformylation systems with the common used
surfactant CTAB the descriptions of solutions for the catalyst product separation are very
limited in literature.
Surfactants that fulfil that requirement are polyoxyethylenes (ref 9). The separation
occurs when the mixture is cooled. The stable emulsion separates into an aqueous phase
and organic phase, when the system is cooled.
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4.4 Supported rhodium complexes on silica nanoparticles
Another solution to separate the catalyst in hydroformylation is provided by
nanoparticles. However literature does not provide much research, it can be a good
alternative for the current processes. In this case the catalyst is supported by non-porous
fumed-silica nanoparticles for SAPC (supported aqueous phase catalyst), see ref. 11,12
and 13. Highly dispersed fumed silica’s are normally used as fillers, additives and
medicinal- and industrial adsorbents.
Supported aqueous-phase catalysis shows high capacity in the conversion, selectivity and
also the easy recovery of the catalyst from the organic phase. In this system, the catalyst
is immobilized in a thin water layer adhered within the pores of high surface area
silicates. Using this system, one can convert higher olefins at relative high rates, without
metal leaching (loss of catalyst).
An important problem however is the hydration of the catalyst. The fumed silica particles
have low amounts of hydroxyl groups. In an aqueous suspension the active sites of the
fumed silica form strong hydrogen bonds with water molecules.
4.4.2 Results
Several experiments have been performed in literature and the most interesting results are
highlighted in this paragraph (ref. 11).
The performances of 1-hexene hydroformylation using SAPC are shown in table 4.5. For
comparison, the results of the conventional biphasic catalyst system have been listed also.
Specifications of the experiments are given in the table.
After reaction there existed a slurry aqueous catalyst layer, containing non-porous fumed
silicas, Rh-complexes, uncoordinated TPPTS and water. The upper layer of products was
separated from the slurry catalyst layer by decantation.
In all cases, the selectivity towards heptanal was approximately 100%. The use of fumed-
SiO2 SAPC shows good catalytic performance, it is comparable with the conventional
biphasic system, with CTAB surfactant. The silica particles are defined as FA, GA or
GB, the properties of these particles are listed in table 4.5. Porous SiO2 (GB) and large
particles with relative small specific surfaces (SiO2-GA) however shows a negative effect
on the reaction rate.
19
The rhodium content in the organic phase in the case of the fumed-SiO2, on the other
hand was about one magnitude lower than that in the conventional system (compare first
and last experiment, rhodium leaching).
The experiments are performed at an agitation speed of 400 rpm. The reaction rate
increased linearly with agitation speeds between 100 – 400 rpm. Above 400 rpm the
reaction rate is not influenced.
Further testing is performed with the non-porous fumed silica. The influence of structure
and particle size was investigated. Smaller particle size and higher surface areas are
beneficial for the reaction rate and the linear/branched ratio, table 4.6.
Table 4.6: comparison of 1-hexene hydroformylation with several kinds of fumed-SiO2-SAPC
Support SBET (m2/g) Mean diameter (nm) Conversion (%) n/i STY (mmol/h gRh) TOF (h-1)
SiO2-FA 361 16 69.3 3.3 4210.5 433.3
SiO2-FB 193 12 62.2 3.0 3777.2 388.7
SiO2-FC 393 14 72.2 3.3 4399.0 452.7
SiO2-FD 361 17 47.7 3.4 2894.6 297.9
SiO2-FE 232 13 53.3 3.1 3234.8 332.9
SiO2-FF 189 16 51.2 3.3 3112.5 320.3
Reaction conditions: T=373K, CO/H2= 1/1 (v/v), P= 4 Mpa, [Rh]= 4x10-5 mol, TPPTS/Rh = 10 mol/mol, agitation speed= 400 rpm,
SiO2= 2 gr. support hydration = 50 wt%, 1-hexene = 0.1 mol, toluene = 38.0 ml, reaction time= 4 h.
Other important parameter are the olefin/Rh molar ratio (maximum reaction rate is
reached 2500 at 373 K ant 4 MPa) and the pressure. The olefin/Rh ratio has a small
influence on the n/i aldehyde ratio.
This suggests that the adsorption ability of the fumed silica in respect to the TPPTS-Rh
complexes and TPPTS would be conceivably high.
A drop of the total pressure cause the decrease of syngas concentration and the relative
ratio of syngas/phospine concentration in the catalyst layer, which is an advantage for the
competitive coordination of phosphine rather than CO on rhodium atom. This is
favourable for the formation of active rhodium species with more phosphine ligands.
Lower pressure thus results in lower conversion but better micro-circumstances to form
linear aldehydes, as in figure 4.9.
20
Reaction conditions: L/Rh = 50 mol/mol, P=1
MPa, reaction time 2 h., others same as in table
4.6.
:conversion, :n/i.
Higher catalytic performance comparable to that of the conventional biphasic system was
achieved by using non-porous fumed SiO2-SAPC for 1-hexene hydroformylation. The
rhodium content (by catalyst leaching) in the organic phase was about one magnitude
lower than that in biphasic system.
The SAPC system provides a possibility that the catalyst can operate efficiently in a wide
range of support hydration range from 40 to 64 wt%, keeping a high reaction rate and
selectivity.
The structure of support has been confirmed to be the key issue in the performance of
SAPC. The SAPC prepared by using fumed SiO2 with smaller particle size and larger
surface area provided beneficial contribution to the catalytic performance.
4.5.2 Results
The main goals are to maintain a high hydroformylation activity and a good separation of
the catalyst after the reaction. Therefore the solubility of different ligands in organic
solvents is determined at room temperature. These results are summarized in table 4.7.
22
It can be concluded that OPGPP with increasing molecular weight (with R = 58, see
figure 4.11) has decreasing solubility in heptane. From the point of catalyst recovery,
apolar solvent such as heptane is preferred for non-aqueous homogeneous catalysis.
This is confirmed in experiments with other solvent than heptane. The solvents toluene,
1,4-dioxane and anisol give high conversions as heptane. The colour of the reaction
mixture with toluene and 1,4-dioxane and anisol turned however out to be slightly
yellow, indicating loss of catalyst in the reaction mixture. This confirms the choice of
heptane as solvent. This is probably the result of different solubility of phosphines in the
solvents.
Another important parameter is the ratio phosphine/rhodium. The best results for the
hydroformylation of 1-decene were obtained at a molar ratio >13. Below 13 the
conversion decreases and there will be loss of catalyst, indicated by the colour of the
mixture. Addition of TPP (triphenylphosphine) caused an increase in the n/iso ratio,
which is preferred for most products. This seems no good solution to raise the n/iso ratio
because a slight loss of catalyst was induced, because TPP dissolves more in the solution.
See table 4.9 for the results.
Table 4.9: Effect of OPGPP/Rh (mol) ratio and triphenylphosphine on the reaction
OPGPP/Rh (mol) PPh3/Rh Conversion (%) Aldehyde yield (%) n/iso ratio
3 75.3 73.5 0.94
7 90.0 88.3 0.96
13 99.4 97.6 0.94
30 99.7 98.9 0.99
3 3 54.3 53.2 0.98
13 4 94.0 93.1 1.3
13 13 95.5 94.6 1.8
Reaction conditions: 1-decene 2.0 ml., heptane 4.0 ml., internal standard 0.3 m, Rh(acac)(CO)2 1.058x10-5 mol, P(CO)/P(H2) = 1:1, T
=90 oC, syngas pressure 5.0 MPa, reaction time 4 h.
The goal is to recycle the catalyst; therefore successive reaction runs have been
employed. Separation takes place by cooling the mixture to room temperature and use
23
decantation to separate the insoluble solvent and catalyst/ligand complex. Loss of
phosphite in the organic phase was determined by ICP technique.
In the experiments the separated catalyst was reused up to six times without significant
decrease in activity. In the first two reaction runs there was a loss of P of 7.8 and 7.2 %.
In the following runs the loss decreased, which is showed in table 4.10.
This decrease in loss of P is ascribed to the weight distribution of the polyether group in
the ligand molecule. Polyether derivatives are mixtures of different weight compounds,
according to table 4.7 phosphates of lower weight have higher solubility.
Not only 1-decene can be converted in an aldehyde using OPGPP ligand, but also other
olefins. This results in increasing aldehyde yield and n/iso ratio for olefins with
decreasing chain length.
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4.6 Remaining techniques
In this paragraph some of the remaining interesting techniques are discussed shortly. The
reason to mention these techniques shortly is because little information is found in
literature or the articles are a bit old.
Techniques described are: hydroformylation with ruthenium catalyst, high pressure
effects of homogeneously catalyzed hydroformylation and sulfonated xantphos ligand.
25
faster through the aqueous phase and have therefore more interaction with the organic
reactant phase. Experiments are performed at normal hydroformylation conditions, only
the pressure is higher, 50 bar. The results using interacting cyclodextrins are very
promising for 1-octene hydroformylation; the conversion is 90 % with aldehyde
selectivity to 99 %. Also the linear to branched ratio is better than in normal
hydroformylation, l/b is about 20. Reaction rate however are not yet very satisfying,
because experiment took 24 hours.
The conclusion is that sulfonated xantphos ligand appears to be a valuable ligand in
combination with a biphasic system with addition of the right cyclodextrins. Separation
of the catalyst is also possible because it is a biphasic system. Methods to separate are
described earlier in this thesis, but not in the found literature about xantphos ligands.
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5. Discussion
In this final chapter the described new techniques in hydroformylation will be discussed.
In the literature and articles that are used for this report, a lot of different research and
developments are described. All these different techniques are presented and tested on
laboratory scale. Little is known whether these methods can be used on commercial scale.
Therefore advantages and disadvantages of the described systems in chapter 4 will be
compared with the current processes described in chapter 3.
27
Small disadvantages of the system are the micellar phase and the separation of the
catalyst. Behaviour of the micellar phase (stability, size and micelle shape) is rather
complex and depends on many parameters. A lot of research is needed to obtain optimal
selectivity in combination with reaction rates.
Separating the product and catalyst can be achieved by cooling the mixture and use
decantation to separate organic and aqueous phase. The presence of surfactants
complicates the phase separation, because the separation with surfactant is not as neat as
with ordinary biphasic systems. This causes a slight loss of catalyst or product.
Using another catalyst like ruthenium is not very probable, because the whole industry is
based on cobalt and rhodium. Ruthenium has also lower activity although the better
linearity. Other provided techniques are more probable than this one.
The hydroformylation with high pressures up to 700 MPa is not yet a good alternative,
because hydroformylation does not occurs significant better. Costs most likely will be
higher than the benefits. Only when there is a market for high value products made by
high pressure hydroformylation has a future.
28
In contrary of the other two, the use of sulfonated xantphos ligand in combination with
cyclodextrins in a biphasic system has a future. This is due to the high conversions and
linearity. This research is yet only at the beginning and it will take same time to develop.
29
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30
Appendix I:Process flow diagrams of industrial processes
BASF process
Exxon process
31
Shell process
RCH/RP process
32
UCC process, liquid recycle
33
Appendix II: Rhodium catalyst cycle
34