Ethylene Hydroformylation in the Presence of Rhodium Catalysts in Hydrocarbon-Rich Media: The Stage of Combined Conversion of Refinery Gases to Oxygenates

Article abstract of DOI:10.1134/S0965544119090056

Abstract: The feature of hydroformylation of model gas mixtures with different ethylene, hydrogen, and methane concentrations in the presence of rhodium catalysts have been studied. The effect of the initial pressure in the reactor and the reaction temperature on the reaction rate and selectivity has been determined. It has been shown that ethylene hydroformylation occurs with a high propanal selectivity (up to 99%), with the turnover frequency of the reaction reaching 9500 h^–1. It has been proposed that various phosphine ligands should be used to implement alternative methods of separating the catalyst system from the reaction products.

Full text of DOI:10.1134/S0965544119090056

ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, No. 9, pp. 1009–1016. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Neftekhimiya, 2019, Vol. 59, No. 5, pp. 560–568.
Ethylene Hydroformylation in the Presence of Rhodium Catalysts
in Hydrocarbon-Rich Media: The Stage of Combined Conversion
of Refinery Gases to Oxygenates
a,
a
a
a
a
D. N. Gorbunov *, M. V. Nenasheva , R. P. Matsukevich , M. V. Terenina , F. N. Putilin ,
a,
b
a
Yu. S. Kardasheva *, A. L. Maksimov , and E. A. Karakhanov
a
Faculty of Chemistry, Moscow State University, Moscow, 119234 Russia
b
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: suskab_91@mail.ru
Received March 14, 2019; revised May 10, 2019; accepted May 13, 2019
*
Abstract—The feature of hydroformylation of model gas mixtures with different ethylene, hydrogen, and
methane concentrations in the presence of rhodium catalysts have been studied. The effect of the initial pres-
sure in the reactor and the reaction temperature on the reaction rate and selectivity has been determined. It
has been shown that ethylene hydroformylation occurs with a high propanal selectivity (up to 99%), with the
–1
turnover frequency of the reaction reaching 9500 h . It has been proposed that various phosphine ligands
should be used to implement alternative methods of separating the catalyst system from the reaction products.
Keywords: cracked gases, ethylene, methane, hydroformylation, oxygenates, fuel additives, oxygen-contain-
ing products, propanal, phosphine ligands, catalyst recycling
DOI: 10.1134/S0965544119090056
INTRODUCTION
fairly high amount of hydrogen and carbon monoxide
Fig. 1, flows II–IV); therefore, oxygen-containing
compounds can be synthesized directly from the
resulting gas mixtures, without constructing a separate
plant for synthesis gas production [7–11]. The choice
of the conversion method largely depends on the com-
position of the feed refinery gas.
(
Deep conversion of fossil hydrocarbons (HCs) is
still an issue of current concern. At oil refineries
equipped with HC cracking units, a significant
amount of ethylene and saturated C + gases is
2
formed in addition to target commercial products;
most commonly, these gases are combusted to gener-
ate heat [1–5]. This utilization cannot be considered
It should be noted that saturated HCs are also
rational, taking into account the large number of formed in each of the above processes. There are pub-
purification and preparation stages (drying, desulfur- lished data on hydroformylation processes in media
ization) to which the feedstock is subjected and the enriched in carbon dioxide or lower HCs (Gas
low heat output during the combustion of mixtures of Expanded Liquids, GXLs) [12–17]. It was reported
this composition [6]. Currently, methods to convert that an increase in the total pressure in a hydroformy-
light HCs to high value-added products, such as oxy- lation reactor owing to gas supply contributes to a bet-
genates, are being actively searched for. Integration ter saturation of the solvent with the reacting compo-
of gas conversion with the currently available pro- nents—olefin, carbon monoxide, and hydrogen—and
duction processes will make it possible to increase thereby has a positive effect on the reaction rate. The
the feedstock conversion depth, improve the eco- physicochemical constants of gases, such as critical
nomic indicators of production, and expand the temperature T and pressure P , determine the degree
c
c
range of products manufactured by the enterprises.
of expansion of the liquid phase. Under the reaction
Catalytic cracker gases can contain a certain conditions (high pressures and temperatures), the
amount of ethylene; however, to provide ethylene expansion of the liquid phase volume owing to gas
hydroformylation, it is necessary to feed synthesis gas condensation can be 40–80% of the initial volume;
to the reactor (Fig. 1, flow I). The implementation of therefore, the consumption of the solvent can be
conversion processes using the membrane-assisted decreased. Using the example of the hydroformylation
ethylene concentrating, oxycracking, and matrix- of propylene of the propane–propylene fraction, it
assisted conversion technologies leads to the forma- was shown that the reactions in GXLs (using toluene,
tion of ethylene-enriched gas mixtures containing a butanol-1, and NX-795 (butanal oligomer mixture) as
1009

1010
GORBUNOV et al.
Synthesis gas
Propanol-1
Hydrogenation
Propanal
Refinery gas
Purification
(up to 20% ethylene)
I
Hydrogenation
II
III
IV
Oxycracking
Aldol
condensation and
hydrogenation
Matrix-assisted
conversion
С alcohol
6
Membrane-assisted
ethylene concentrating
Fig. 1. Routes of the combined conversion of refinery gases.
solvents) exhibit a higher selectivity for linear aldehyde bon monoxide used in the study were purchased from
12]. The implementation of the hydroformylation of Voessen.
[
propylene mixed with propane without the compo-
nent separation stage is a more cost-effective process
in terms of energy consumption; in this case, the pro-
pane-enriched stream from the hydroformylation
reactor can be recycled to produce an additional
amount of propylene. An advantage of the use of
GXLs as alternative reaction media over the use of
supercritical fluids is that gases should not be neces-
sarily compressed to a high pressure [12].
Liquid products were analyzed by gas–liquid chro-
matography on a Khromos chromatograph equipped
with a flame ionization detector and a 50-m-long cap-
illary column coated with the SE-30 phase using tem-
perature programming of 60–230°C, helium as a car-
rier gas, and n-heptane as an internal standard. Anal-
1
31
ysis by H and P nuclear magnetic resonance (NMR)
spectroscopy was conducted on a VarianXL-400
instrument with an operating frequency of 400 MHz.
Matrix-assisted laser desorption/ionization (MALDI)
spectra were recorded on a Bruker Daltonics Autof-
lexII MALDI/time-of-flight mass spectrometer with
a nitrogen laser at a working wavelength of 337 nm.
The matrix was 2,5-dihydroxybenzoic acid.
This study is focused on the features of the ethylene
hydroformylation reaction in gas mixtures enriched in
saturated HCs (methane). The effect of the feed gas
mixture composition, the initial pas pressure in the
reactor, and temperature on the reaction rate and
selectivity is studied. The catalyst system components
are rhodium complexes with phosphine ligands, which
make it possible to separate the catalyst from the reac-
tion products by various methods.
Polyethylene Glycol (PEG)–PPh Phosphine
3
Ligand Synthesis Procedure
Initially, 0.5 g (1.62 mmol) of 4-(diphenylphos-
phino)benzoic acid and 5 mL of dichloromethane
were placed in a round-bottomed flask equipped with
a magnetic stirrer in an argon atmosphere. Twenty
EXPERIMENTAL
Triphenylphosphine trisulfonate (triphenylphos- milligrams (0.16 mmol) of 4-dimethylaminopyridine
phine-3,3',3''-trisulfonic acid trisodium salt (TPPTS)), and 2 g (0.67 mmol) of PEG (M = 3000 g/mol) were
polyethylene glycol (M = 3000 g/mol), 4-(diphenyl- added to the solution under stirring. The mixture was
phosphino)benzoic acid, and 1,3-dicyclohexylcarbo- cooled to 0°C; after that, 0.34 g (1.65 mmol) of 1,3-
diimide (Sigma-Aldrich) were used without further dicyclohexylcarbodiimide was added. The solution
purification. The Rh(acac)(CO) complex was syn- was stirred at 0°C for 5 min and then at room tempera-
2
thesized as described in [18]. Solvents (toluene, acety- ture for 3 h. Upon the completion of the reaction, the
lacetone) were prepared in accordance with standard precipitate was filtered off on a paper filter and washed
procedures. Ethylene, hydrogen, methane, and car- with dichloromethane. A tenfold excess of cooled
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ETHYLENE HYDROFORMYLATION IN THE PRESENCE OF RHODIUM CATALYSTS
1011
diethyl ether was added to the filtrate; the resulting ether, and dried in an argon atmosphere. The resulting
precipitate was filtered off on a glass-filter funnel in an substance was a light yellow powder. The product yield
argon atmosphere, washed three times with diethyl was 1.9 g (85% of the theoretical yield).
c
c
b
b
O
b
b
c
c
a
O
O
P
P
O
nO
a
O
PEG-PPh3
b
b
b
b
P
b
2
1
H NMR (400 MHz, CDCl ) δ: 3.40–3.90 (m,
Catalytic Ethylene Hydroformylation Procedure
3
3
7
10H, –(CH –CH –O) –), 4.45 (m, 4H, H ), 7.27–
.38 (m, 24H, H ), 7.94–7.99 (m, 4H, H ) ppm.
Reactions were run in a 25-mL ParrInstrument steel
2
2
n
a
autoclave equipped with a mechanically driven stirring
device (magnetic coupling), a gas-trapping stirrer, and a
device for thermostating at temperatures of up to 350°C.
b
c
31
P NMR (162 MHz, CDCl ) δ: –4.95 ppm.
3
Mass spectrum (MALDI): molecular mass distri- The autoclave was charged with 4.0 mL of the solvent
bution maximum m/z = 3560.
(toluene), catalyst system components—0.015 mmol of
Rh(acac)(CO) and 0.045 mmol (in terms of phos-
2
phorus) of the phosphine ligand,—and 0.6 mL of the
internal standard (n-heptane). The autoclave was two
times flushed with carbon monoxide and sequentially
filled with methane to a predetermined pressure and
then with carbon monoxide, hydrogen, and ethylene
to predetermined pressures. The total pressure was
controlled using the sensor of a Teledyne syringe
pump. After that, stirring was turned on (1000 rpm);
the autoclave was heated at a rate of 3°C/min and then
held at a given temperature. Reaction was run under
permanent stirring for a predetermined time, while
recording the dependence of pressure and temperature
on the reaction time. Upon the completion of the
reaction, the autoclave was cooled to room tempera-
ture to record the readings of the pressure gage (error
of 2 atm); after that, the autoclave was depressurized to
take a sample for analysis.
Table 1. Possible composition of gas mixtures supplied
to the hydroformylation stage during the combined con-
version of refinery gases
Component
Stream 1
Stream 2
Stream 3
H2
20.3
0.0
0.0
40.6
0.4
4.1
0.0
O2
N2
1.1
0.0
CO
CO2
CH4
C H
10.4
1.7
12.6
0.8
6.6
0.1
43.3
0.2
5.9
25.1
4.7
41.2
13.4
25.5
0.0
2
6
4
2
8
6
C H
12.0
1.5
2
C H
0.0
0.0
0.3
2
C H
0.5
1.7
3
RESULTS AND DISCUSSION
C H
0.6
2.8
3
Table 1 shows examples of gas mixtures from com-
bined refinery gas conversion units. The composition of
the product gas mixture depends on the feed refinery
gas composition (methane, fatty gas, and olefin con-
centrations), the selected combined conversion route,
and partial oxidation conditions, such as the residence
time of the feedstock in the reactor, temperature, pres-
sure, and feedstock consumption rate [7, 19].
The implementation of the operating mode of the
combined units (Fig. 1) makes it possible to control
the composition of the gas mixtures supplied to the
oxosynthesis stage. Therefore, the hydroformylation
of model mixtures listed in Table 2 was studied. Meth-
C4+
0.0
0.1
0.5

Table 2. Composition of the model gas mixtures
Component composition, vol %
Model mixture no.
C H
CO
H2
CH4
2
4
1
2
3
20
20
40
20
20
20
40
20
20
20
40
20
PETROLEUM CHEMISTRY Vol. 59 No. 9 2019

1012
GORBUNOV et al.
Table 3. Comparison of the physicochemical parameters of lower HCs
Physicochemical constants
Measurement
conditions
Expansion,
V(T,P)/V0
Gas
Reference
[14]
Тc, °С
Рc, atm
CO2
31.0
–83.7
96.6
73.8
42.6
42.5
37.0
40°C, 20 atm
1.45
Not available
1.4
Methane
Propane
Butane
80°C; 12 atm
160°C; 70 atm
[12]
[13]
152.0
1.4
ane was used as saturate HC component. Table 3
Currently, about 50% of all industrial oxosynthe-
shows the physicochemical constants of gases that sis processes are implemented using modified rho-
were previously used as media to study the hydro- dium–phosphine complexes; the reaction products
formylation of olefins.
(aldehydes) are separated from the catalyst solution
Depending on T and P of gases, the liquid (sol- by the distillation method. Alternative methods for
c
c
vent) can expand owing to the absorption of the gases; the separation and recycling of catalyst systems are
the relative expansion of the liquid (V/V ) depends on based on the use of water-soluble ligands in two-
0
the gas pressure and temperature. To generate GXLs, phase systems, temperature-controlled ligands, and
it is advantageous to use gases whose critical tempera- ionic liquids and the separation of the catalytic com-
ture is slightly lower than the temperature of the stud- plex by extraction and membrane nanofiltration pro-
ied reaction [12, 13]. Data in Table 3 suggest that, in cesses [20–23]. The catalyst systems used in this
the case of methane, a significant saturation and study comprised a catalyst precursor—rhodium com-
expansion of the liquid is scarcely probable. However,
since the presence of methane in the system leads to an
increase in the total pressure, the dissolution of gas-
eous reactants (C H , CO, and H ) in toluene, along
plex Rh(acac)(CO) —and phosphine ligands provid-
ing the isolation of catalyst systems from reaction
mixtures by various methods.
2
2
4
2
with their contact with the homogeneous catalytic
complex, is more effective.
A general scheme to describe possible chemical
conversions during hydroformylation is shown below.
Catalyst
Solvent, Т
H
+
+
CO + H2
A
B
O
O
C
O
OH
Schematic hydroformylation of ethylene.
The reaction results in the formation of propanal (A), Figure 2 shows the reaction profile for the hydro-
diethyl ketone (B), and aldol (C).
formylation of model mixture 1 (dependence of the
Using the example of the hydroformylation of gas pressure in the reactor on the reaction time) at an
model mixtures 1–3 in the presence of a classical initial gas pressure of 100 atm under heating from 25 to
Rh/PPh catalyst system, the effect of the total initial 80°C at a rate of 3°C/min. The figure also shows a
3
pressure and reaction temperature was studied. In the thermal expansion curve of methane (dotted line),
study, the absorption rate of gaseous components— which characterizes the pressure in the reactor pro-
ethylene (substrate, S), CO, and H —was determined vided that the reaction and gas absorption do not
2
form the pressure drop in a stationary reactor under occur.
uniform heating from room temperature to a given
A temperature of 55°C corresponds to the onset of
temperature. The kinetics of ethylene and propylene
the reaction; an almost complete absorption of the
gaseous components is achieved by the time at which
the reaction mixture is heated to 80°C. The efficiency
hydroformylation reactions in the presence of rho-
dium catalysts was studied in detail in [24, 25]; there-
fore, the aim of this study was to obtain data on the
–1
effect of saturated HC components and the composi- of the catalyst system (turnover frequency (TOF), h )
tion of model gas mixtures on ethylene conversion. for the curve portion that describes the most rapid
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ETHYLENE HYDROFORMYLATION IN THE PRESENCE OF RHODIUM CATALYSTS
1013
P, atm
Thermal expansion of HC gas
120
P(init. at 25°С) = 100 atm
P(init. at 25°С) = 41 atm
100
Occurrence
of reaction
Heating 25–55°С
ΔT = 55–80°C
80
T = 80°C
60
0
10
20
70
80
t, min
Fig. 2. Reaction profile for the hydroformylation of model mixture 1. Reaction conditions: Rh(acac)(CO) , 4 mg; PPh , 12 mg;
2
3
S/Rh = 1600; toluene, 4 mL; heptane, 0.6 mL; P = 100 atm; heating rate, 3°С/min; and T = 80°С.
init
fin
P, atm
20
(a)
P, atm
60
(b)
1
P(init. at 25°С) = 100 atm
P(fin. at 25°С) = 40 atm
P(init. at 25°С) = 50 atm
P(fin. at 25°С) = 23 atm
1
00
50
40
30
Heating 25–55°С
Heating 25–55°С
8
0
T = 60°C
T = 80°C
Occurrence
of reaction
ΔT = 55–80°C
6
0
Occurrence
of reaction
ΔT = 55–60°C
0
10
20
30
90
t, min
0
10
20
30
90
t, min
Fig. 3. Reaction profile for the hydroformylation of model mixture 1: (a) at a temperature of 60°C, an initial pressure of 100 atm,
and S/Rh = 1600 and (b) at a temperature of 80°C, a pressure of 50 atm, and S/Rh = 800. Reaction conditions: Rh(acac)(CO) ,
2
4
mg; PPh , 12 mg; toluene, 4 mL; heptane, 0.6 mL; and heating rate, 3°С/min.
3
–1
occurrence of the reaction was 9500 h ; it was deter- tion. In this case, the formation of the hydrogenation
mined by formula (1):
product—ethane—is negligible and scarcely probable
because the threshold of activation energy for the
hydrogenation reaction is higher than that for the
hydroformylation reaction [25]. The reaction rate sig-
nificantly decreases, while the gaseous reagents are
consumed and their residual concentrations become
low; however, the reaction occurs to nearly complete
conversion of the gaseous reagents; the presence of
methane in the system contributes to a better dissolu-
n (reacted ethylene)
TOF =
.
(1)
n(Rh)treaction
The amount of reacted ethylene (in mol) was deter-
mined by the equation of state for gases using the
residual pressure values. The formation of a single
product—propanal (A)—was recorded; the amount of
this product corresponds to the stoichiometric reac-
PETROLEUM CHEMISTRY Vol. 59 No. 9 2019

1014
GORBUNOV et al.
P, atm
60
50
40
30
mixture 1 (Pinit = 50 atm, Pfin = 23 atm)
mixture 2 (Pinit = 50 atm, Pfin = 32 atm)
(Pfin at T = 25°C, after cooling)
Heating 25–55°С
Occurrence of reaction
ΔT = 55–80°C
T = 80°C
0
20
70
80
t, min
Fig. 4. Reaction profile for the hydroformylation of model mixtures 1 and 2. Reaction conditions: Rh(acac)(CO) , 4 mg; PPh ,
2
3
1
2 mg; S/Rh = 800; toluene, 4 mL; heptane, 0.6 mL; P = 50 atm; heating rate, 3°С/min; and T = 80°С.
init fin
tion of the gases and their transfer to the active sites of 99%). The residual pressure of gas mixture 2 (meth-
the catalyst.
ane-enriched) was 32 atm, 20 atm of which are
Figures 3a and 3b show reaction profiles for the accounted for the pressure of methane and the
hydroformylation of model mixture 1 (a) at a tempera- remaining 12 atm are attributed to the pressure of a gas
ture of 60°C and an initial pressure of 100 atm and mixture of ethylene with carbon monoxide and hydro-
(
b) at 80°C and an initial pressure of 50 atm.
gen; 20% of diethyl ketone and 80% of propanal were
A decrease in the final reaction temperature from identified in the products. The more gently sloping gas
8
0 to 60°C leads to an increase in the complete eth- pressure variation curve in the hydroformylation of gas
–1
ylene conversion time (TOF = 6000 h ) and the for- mixture 2 also suggests that, for the mixture that is not
mation of a diethyl ketone–propanal mixture in a ratio enriched in hydrogen, the reaction rate is lower,
of 1 : 10. The implementation of a similar reaction although an identical temperature is required for the
with holding of the reaction medium at a final tem- onset of the reaction in the two cases.
perature of 120°C contributes to the occurrence of
Model mixture 3 represents an approximate com-
aldol condensation to form aldol (C); the aldol con-
tent in the final mixture achieves 48%. With a decrease position of industrial gas mixtures enriched in eth-
in the initial pressure of mixture 1 fed to the reactor to ylene; these mixtures contain ethylene in excess rela-
5
0 atm, the reaction profile and selectivity vary only tive to the amount of both carbon monoxide and
slightly.
hydrogen. In the study, the hydroformylation of model
The hydroformylation of model mixtures 1 and 2 mixture 3 was run in the presence of the rhodium–
made it possible to determine the effect of excess phosphine catalyst (Rh(acac)(CO) + PPh ) in tolu-
hydrogen on the reaction rate and selectivity (Fig. 4).
2
3
ene at temperatures of 60 and 80°С (Table 4). In this
Excess hydrogen contributes to an increase in the case, in addition to propanal, diethyl ketone was
reaction depth and the propanal selectivity (up to formed (15 and 20%, respectively).
Table 4. Hydroformylation of model mixture 3 at temperatures of 60 and 80°С*
Reaction selectivity, %
TOF, h–1
T, °C Pinit, atm P , atm Ethylene conversion, %
fin
propanal (А)
diethyl ketone (B)
6
8
0
0
75
75
40
35
78
90
85
80
15
20
3700
6500
*
Reaction conditions: Rh(acac)(CO) , 4 mg; PPh , 12 mg; S/Rh = 2400; toluene, 4 mL; heptane, 0.6 mL; and heating rate, 3°C/min.
2 3
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ETHYLENE HYDROFORMYLATION IN THE PRESENCE OF RHODIUM CATALYSTS
1015
P, atm
Rh(acac)(CO)2 + PPh3 (Pfin = 41 atm)
1
00
Rh(acac)(CO)2 + TPPTS (Pfin = 49 atm)
Rh(acac)(CO)2 + PEG-PPh3 (Pfin = 43 atm)
(Pfin at T = 25°C after cooling)
Heating
5–55°С
2
8
0
60
ΔT = 55–80°C
T = 80°C
0
10
20
30
40
50
60
100
120
130
t, min
Fig. 5. Reaction profile for the hydroformylation of model mixture 1 with different ligands. Reaction conditions: Rh(acac)(CO) ,
2
4
mg (0.015 mmol); ligand, 0.045 mmol; S/Rh = 1600; toluene, 4 mL; heptane, 0.6 mL; P = 50 atm; heating rate, 3°С/min;
init
and T = 80°С.
fin
–1
The experimental data on the hydroformylation of the catalyst system with a TOF value of 3500–9500 h .
model mixtures 1–3 suggest that industrial gas mix-
tures enriched in inert HCs (in particular, methane)
can be converted to various oxygenates by hydro-
formylation in the presence of a rhodium–phosphine
catalyst; in this case, acceptable reaction rates and
propanal selectivities are achieved at reaction tem-
peratures of 60–80°C and initial pressures of the gas
In the described examples, a homogenous catalyst can
be separated from the reaction products only by the
distillation method, which has some known disad-
vantages; therefore, the hydroformylation of model
mixture 1 was studied using phosphine ligands pro-
viding the isolation of the catalyst system from
mixture of 50–100 atm. The steepest portions of the homogeneous media by alternative methods; the
gas absorption curves correspond to the efficiency of ligands are shown below.
SO Na
3
P
O
NaO3S
P
O
(
CH CH O)
2 2 n
O
P
SO Na
3
PEG-PPh3
TPPTS
Polyethylene glycol–PPh is a macromolecular case of TPPTS, the onset of the reaction is slightly
3
ligand synthesized by modifying PEG with an average shifted to the region of higher temperatures (onset of the
molecular mass of 3000 g/mol; TPPTS is sodium reaction at Т ≈ 70°C); at low reactant concentrations,
triphenylphosphine trisulfonate. It was previously the decrease in the rate is more significant than that in
found [26] that the PEG–PPh macromolecular the case of PPh and PEG–PPh . This finding can be
3
3
3
ligand can be isolated from the reaction medium by attributed to the presence of water in the system and the
nanofiltration using membranes whose pore size does fact that the catalyst is in the aqueous phase. The solu-
not exceed 2 nm. It is known that TPPTS is a water- bility of the reactants in this system is lower than that in
soluble ligand; using TPPTS, hydroformylation is pure toluene; the rate-limiting step can be the reactant
implemented in a water–organic solvent two-phase transfer to the interface, where the catalytic reaction
system [27].
occurs. The variation in the ligand does not affect the
Figure 5 shows comparison of the reaction profiles reaction selectivity; in each case, propanal was identi-
in the presence of the different catalyst systems. In the fied as the main product in the liquid phase (98–99%).
PETROLEUM CHEMISTRY Vol. 59 No. 9 2019

1016
GORBUNOV et al.
Table 5. Correlation of catalyst systems and hydroformylation methods
Catalyst system
Process
Catalyst separation and recycling
Prototype
Rh/PPh3
Continuous-running
Distillation, recycling of the catalyst solution stream
Nanofiltration
[28]
[29]
[30]
Rh/PEG–PPh3
Rh/TPPTS
Phase separation
CONCLUSIONS
12. D. Liu, V. R. Chaudhari, and B. Subramaniam, Chem.
Eng. Sci. 187, 148 (2018).
In the studies, optimum conditions for the hydro-
formylation of ethylene-containing gas mixtures
enriched in HC gases have been determined. The
studied catalyst systems can be correlated (Table 5)
with a process in which this stage of the combined
1
3. D. Liu, Z. Xie, W. K. Snavely, et al., React. Chem. Eng.
3
, 344 (2018).
14. H. Jin and B. Subramaniam, Chem. Eng. Sci. 59, 4887
(2004).
conversion of refinery gases to oxygenates can be 15. D. Liu, V. R. Chaudhari, and B. Subramaniam, AIChE
implemented with the highest efficiency and the low-
est costs. It has been found that, in the hydroformyla-
tion of hydrogen-enriched mixtures in the presence of
rhodium–phosphine catalysts, propanal is formed as
the main product (up to 99%), while the formation of
diethyl ketone (up to 20%) occurs if ethylene is present
in the mixture in a molar excess relative to CO.
J. 64, 970 (2018).
16. B. Subramaniam, V. R. Chaudhari, S. A. Chaudhari,
et al., Chem. Eng. Sci. 115, 3 (2014).
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Translated by M. Timoshinina
PETROLEUM CHEMISTRY
Vol. 59
No. 9
2019