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Hydrogenation of fatty acid methyl esters to fatty alcohols at supercritical

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Article  in  Journal of the American Oil Chemists' Society · November 1999

DOI: 10.1007/s11746-999-0151-y

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 Hydrogenation of Fatty Acid Methyl Esters
to Fatty Alcohols at Supercritical Conditions
Sander van den Harka,*, Magnus Härröda, and Poul Møllerb
a
Chalmers University of Technology, Department of Food Science, c/o SIK, SE-402 29 Göteborg, Sweden,
and bAugustenborggade 21B11, DK-8000 Aarhus C, Denmark

ABSTRACT: Extremely rapid hydrogenation of fatty acid tion of FAME: (i) Hydrogenation of the carbon–carbon dou-
methyl esters (FAME) to fatty alcohols (FOH) occurs when the ble bonds, which can result in saturation of these bonds (Eq.
reaction is conducted in a substantially homogeneous supercrit- 1A), and formation of trans-bonds by isomerization of the
ical phase, using propane as a solvent, over a solid catalyst. At carbon–carbon double bond(s) (Eq. 1B); (ii) hydrogenation
these conditions, the limitations of hydrogen transport are elim- of the carboxyl group (i.e., ester), which leads to either the
inated. At temperatures above 240°C, complete conversion of
formation of a carbonyl (i.e., aldehyde) (Eq. 2) or a hydroxyl
the starting material was reached at residence times of 2 to 3 s,
which is several orders of magnitude shorter than reported in
group (i.e., fatty alcohol) (Eq. 3); (iii) formation of hydrocar-
the literature. Furthermore, formation of by-products, i.e., hy- bons, owing to “overhydrogenation” of fatty alcohols (Eq. 4)
drocarbons, could be prevented by choosing the right process (3,4). The product distribution and pathways followed are
settings. Hydrogen concentration turned out to be the key pa- partly dependent on the catalyst.
rameter for achieving the above two goals. As a result of the su-
percritical conditions, we could control the hydrogen concen- [1A]
tration at the catalyst surface independently of the other process [1B]
parameters. When methylated rapeseed oil was used as a sub-
strate, the hydrogenation catalyst was deactivated rapidly. How-
ever, by using methylated sunflower oil, a catalyst life similar to
that obtained in industrial processes was achieved. Our results
[2]
showed that the hydrogenation of FAME to FOH at supercritical
conditions is a much more efficient method than any other pub-
lished process.
Paper no. J9105 in JAOCS 76, 1363–1370 (November 1999). [3]

KEY WORDS: Copper catalysts, fatty acid methyl esters, fatty

alcohols, heterogeneous catalysis, hydrogenation, propane, su- [4]
percritical.
Saturation of the carbon–carbon double bonds occurs
under relatively mild process conditions. More severe condi-
Fatty alcohols and their derivatives are widely used as surfac- tions are necessary for the hydrogenation of the carboxyl
tants, lubricants, or additives in many industrial products. group, therefore carbon-carbon double bonds are hydro-
Commercially useful alcohols are divided into synthetic and genated before the carboxyl group. Typical conditions for
natural fatty alcohols, the former manufactured from petro- fatty alcohol production are: hydrogen pressures between 200
chemicals. Naturally derived fatty alcohols are produced from and 300 bar, and temperatures ranging from 200 to 300°C
natural fats and oils by hydrogenation of their fatty acids or (5,6).
fatty acid methyl esters (FAME). By the year 2000, natural The reactor throughput under such conditions, expressed
alcohols are expected to account for 65% of the world’s as a liquid hourly space velocity (LHSV), is about 0.2 to 0.3
steadily growing fatty alcohol demand (1). Today, 1 million m3product/m3reactor·h−1 (7). The main problem inhibiting con-
tons a year of fatty alcohols (FOH) are produced (1,2). version is the poor solubility of hydrogen in the liquid phase
The most common process for manufacturing natural FOH (i.e., the FAME) which leads to a lack of hydrogen at the cat-
is the hydrogenation of FAME in the presence of a catalyst. alyst surface. As a consequence, the reaction is limited by hy-
Several reactions occur simultaneously during the hydrogena- drogen transport resistance.
To overcome the solubility problem the reaction can be
performed in a vapor phase, for example in the Davy process
*To whom correspondence should be addressed at Chalmers University of
Technology, Department of Food Science, c/o SIK, P.O. Box 5401, SE-402 (8). The bottleneck in this process is the low concentration of
29 Göteborg, Sweden. E-mail: svh@fsc.chalmers. se FAME in the vapor phase, resulting in a low throughput of

Copyright © 1999 by AOCS Press 1363 JAOCS, Vol. 76, no. 11 (1999)
1364 S. VAN DEN HARK ET AL.

FOH with respect to reactor volume. The problems occurring

in the liquid phase and the vapor phase hydrogenation can be
reduced by using a solvent which has a high solubility for
both reactants. Van de Scheur et al. (9) have shown promis-
ing results using n-octane as a solvent.
To overcome all of the restrictions caused by transport re-
sistance, we have created a substantially homogeneous super-
SCHEME 1
critical phase with almost unlimited access to the catalyst sur-
face for all the reactants (10). This was achieved by introduc-
ing propane into the reaction mixture. At suitable conditions, Robinson equation of state (14). The collected samples were,
propane can completely dissolve both the lipids and the hy- without further preparation, analyzed by silver ion HPLC
drogen (11). For example, for the partial hydrogenation of with gradient elution (15).
methylated rapeseed oil, a 400-fold increase of LHSV (based Definitions: conversion, selectivity, and FOH yield. Three
on substrate) was obtained using this concept (12). definitions are needed to describe the hydrogenation reaction:
In this paper, the reaction rate, selectivity, and productivity First, conversion of the carboxyl group is defined as the molar
for hydrogenation of FAME to FOH at supercritical conditions ratio of all compounds produced by hydrogenation from the
are described as functions of temperature, hydrogen pressure, carboxyl group to the FAME fed to the catalyst bed (=
residence time of FAME in the reactor, and the catalyst life. FAME0).
aldehydes + FOH + hydrocarbons
conversion FAME = 100, in mol/mol% [5]
•

MATERIALS AND METHODS FAME 0

Materials. The starting material consisted of a mixture of sat- Aldehydes, FOH, hydrocarbons, and FAME all refer to the
urated and unsaturated FAME from rapeseed oil (Larodan, mol%, as determined by HPLC analysis of the lipid fraction
Malmö, Sweden) with the following composition (in mol%): of the reaction mixture.
8% methyl stearate, 60% methyl oleate, 21% methyl Second, the selectivity is calculated as the FOH fraction of
linoleate, and 10% methyl linolenate. Propane (instrument the products derived from FAME, and it is calculated as
quality, AGA, Sundbyberg, Sweden) and hydrogen (Hydro- below:
gen Plus 99.995%, AGA) were used in the reaction mixture.
FOH
A chromium-free, copper-based catalyst (Davy Process Tech- selectivity FOH = 100, in mol/mol% [6]
•

aldehydes + FOH + hydrocarbons

nology, Cleveland, England) was used as a fixed bed. The pel-
letized, uniform catalyst was crushed before it was placed, as Third, by multiplying the selectivity and conversion, the yield
a fixed bed, in a high-performance liquid chromatography of fatty alcohol, yieldFOH, can be derived:
(HPLC) tube, with an inner diameter of 4.6 mm and a length
selectivity FOH conversion FAME
• FOH
of 50 or 250 mm. The catalyst bed had a density of 0.95 kg/L. yield FOH = = 100, in mol/mol%
•
[7]
100 FAME 0
No separate activation procedure was performed before start-
ing the hydrogenation. Experimental design and modeling. Conversion, selectiv-
Equipment. A flow sheet for the continuous reactor used is ity, and yield as defined previously are all correlated with,
shown in Figure 1. The amounts of hydrogen and oil were among others, the following variables:
controlled according to previously published principles (13).
Propane and hydrogen were mixed at 80°C, and the oil was conversionFAME = f(Temp, Rtime, PH , Life, Clipid, Ptot, Flow, Catalyst) [8]
2
added at room temperature (Scheme 1, M). This reaction mix-
ture was heated to the desired reaction temperature (Scheme selectivityFOH = g(Temp, Rtime, PH , Life, Clipid, Ptot, Flow, Catalyst)
2
[9]
1, Temp) in an oil bath (Lauda C6 CS, Köningshofen, Ger-
many) and then fed into the HPLC tube filled with catalyst yieldFOH = h(Temp, Rtime, PH , Life, Clipid, Ptot, Flow, Catalyst)
2
[10]
powder (Scheme 1, reactor). After the reactor, samples were
collected from the high-pressure section using a Rheodyne where Temp = temperature (°C); Rtime = residence time(s),
Switching Valve (model 7000, Cotati, CA) (Scheme 1, A). average contact time of FAME with the catalyst; PH2 = hydro-
The pressure was reduced to atmospheric in a pressure reduc- gen pressure (bar); Life = amount of FAME which has passed
tion valve (Scheme 1, P). This valve was used simultaneously a given amount of catalyst (kgFAME/kgcatalyst) (i.e., catalyst
to regulate the propane flow for the purpose of maintaining a life); Clipid = sum of the concentrations of FAME, FOH, alde-
constant residence time in the reactor. The product separated hyde, and hydrocarbons in the reaction mixture (mol%); Ptot
from the gases as a result of the pressure reduction. Finally, = total pressure in the system (bar); flow = total flow of reac-
the gas flow was measured (Scheme 1, F). Knowledge of the tion mixture, propane/hydrogen/lipid, through the reactor
densities of hydrogen and propane was required to control the (mmol/min); and Catalyst, meaning that the equation is valid
composition of the reaction mixture and to estimate the reac- for the catalyst used in the experiments.
tion times. The densities were calculated from the Peng- An experimental design was used to estimate the influence

JAOCS, Vol. 76, no. 11 (1999)

 FATTY ALCOHOL PRODUCTION AT SC-CONDITIONS 1365

TABLE 1
Levels of Variables Used in the Experimental Designa
Levels
Variables Very low Low Medium High Very high
Temperature (°C) 200 220 250 280 300
Hydrogen (bar) 3 10 20 30 37
Residence time (s) 1 1.4 3.4 6.8 11.3
Life (kgFAME/kgcat) 0.25 0.25 0.5 1 1
a
CLipid = 0.105 mol% = 0.75–0.88 wt%; total pressure = 150 bar; total flow rate = 40 mmol/min;
substrate = methylated rapeseed oil (C18:0-3); catalyst = Cu/Zn (particle size = 0.01–2 mm). FAME,
fatty acid methyl ester.

of the process variables on the conversion, selectivity, and diagram. We kept the total flow, the lipid concentration, and
fatty alcohol yield. In the experimental design, we varied the the overall pressure constant. Therefore, all mixtures lie on a
temperature, residence time, hydrogen pressure, and the cata- line (■) parallel to the propane/hydrogen axis. Because of the
lyst life. The variation in these variables was chosen accord- reaction stoichiometry, all reaction mixtures should lie to the
ing to a central composite design, which consisted of a factor- right of the dashed line, where there is enough hydrogen to
ial design augmented with a star (16). Clipid, total pressure, and completely hydrogenate the substrate. Furthermore, the fa-
flow rate were kept constant at 0.105 mol%, 150 bar, and 40 vorable single-phase area (shaded area) becomes larger at
mmol/min, respectively. In total, 25 (= 24 + 1 + 2·4) samples lower temperatures and/or higher total pressures. With this
from 15 experiments were used in the modeling. In the experi- background we chose a total pressure of 150 bar to ensure sin-
ments, the variables were set to levels shown in Table 1. gle-phase conditions in all of the experiments.
Samples were taken at run times equivalent to the set cata- The results of the experiments are summarized in models
lyst life: 0.25, 0.5, and 1 kgFAME/kgcatalyst (not all of these sam- (see Table 2). We selected some contour plots to illustrate
ples belong to the experimental design). The residence time these models (Figs. 2–8). These contour plots can be regarded
was varied by changing the height of the catalyst bed (i.e., the as two-dimensional projections of response surfaces. The out-
amount of catalyst, which ranged from 200 to 2300 mg). liers will be discussed later.
During statistical processing (17) of the experimental re- Conversion and selectivity. At the supercritical conditions
sults, models (i.e., goal functions) were constructed to de- FAME was hydrogenated very quickly. The carbon–carbon
scribe the correlations between the independent variables (xi) double bonds were saturated first (Eqs. 1A,B). This reaction
and the dependent goal functions. These goal functions are is much faster than the hydrogenation of the carboxyl group
conversionFAME, selectivityFOH, and yieldFOH, respectively and occurs readily at temperatures below 200°C with the cat-
(see Eq. 11). alyst used. Hydrogenation of the carboxyl group (i.e., Eq. 5)
4 3 4 4 to alcohols occurred within just a few seconds. Aldehydes, as
goal function = b0 + ∑b x + ∑ ∑b x x + ∑b x x
i =1
i i
i =1 j = i +1
ij i j
i =1
ii i i [11] expected from Equation 2, were not detected. Combinations

The independent variables are: x1, temperature (°C); x2, hy-

drogen pressure (bar); x3, residence time (s, logarithmic
scale); and x4, life (kgFAME/kgcatalyst, logarithmic scale).
The variation between the measured samples and the esti-
mated value of the goal function is given by the standard error
of estimate, SEE. Deviations larger than ± k·SEE are consid-
ered to be significant. k is determined such that k·SEE in-
cludes all variations in our experiments. The effect of varia-
tions in the four variables can be illustrated with contour
plots, i.e., plots showing the value of the goal function as a
function of two variables at constant values of the remaining
variables. We have interpreted the models only within the
range of the high and low levels of the studied variables. Oth-
erwise, the uncertainty in the model would have become too
large.
FIG. 1. Phase diagram for the system fatty acid methyl ester (FAME),
propane, and hydrogen, and the composition of the reaction mixtures
RESULTS AND DISCUSSION (■) used in the experiments. (Stippled area) The estimated single-phase
region at 100 bar and 200°C (11). (---) Indicates the stoichiometric
In Figure 1 the compositions of the different reaction mix- amount of hydrogen needed for complete hydrogenation of the sub-
tures used in the experiments are illustrated in a ternary phase strate into saturated fatty alcohols.

JAOCS, Vol. 76, no. 11 (1999)

1366 S. VAN DEN HARK ET AL.

TABLE 2
Values of the Estimated Parameters in Equation 11 for ConversionFAME, YieldFOH,
and SelectivityFOH
SelectivityFOH
Parametera ConversionFAME YieldFOH at life = 0.25
b0 −1446 −1738 −899
b1 11.3 13.7 7.41
b2 −6.21 −2.71 8.42
b3 429 565 283
b4 −39.0 64.1 —
b12 0.0288 0.0159 −0.0314
b13 −0.588 −1.14 −0.845
b14 — 0.404 —
b23 −0.921 −2.05 −3.38
b24 — — —
b34 18.6 −20.6 —
b11 −0.0222 −0.269 −0.0138
b22 −0.0251 −0.0370 —
b33 −188 −205 −36.1
b44 — — —
k·SEE 1.5·6.5 = 9.6 1.3·5.3 = 6.9 1·6.6 = 6.6
Very low H2
Very low H2 Corner Ac Very low H2
Outliersb Corner Ac Very high temp.e Corner Bd
a
Index: 1, temperature (°C); 2, hydrogen pressure (bar); 3, residence time (s, logarithmic scale); 4, life
(kgFAME /kgcatalyst logarithmic scale): see also Equation 11.
b
Outliers were removed earlier during statistical processing, so the final models did not contain any
outliers.
c
X1 = 220°C, X2 = 30 bar, X3= log(6.8) s, X4 = log(1) kgFAME /kgcatalyst.
d
X1 = 280°C, X2= 30 bar, X3 = log(6.3) s.
e
This point was an outlier also in the general selectivity model. For abbreviation see Table 1.

of low temperature and short residence time resulted in a low is illustrated in Figs. 4 and 5. The decline in the selectivity
conversion of the carboxyl group, whereas at high tempera- was due to the formation of hydrocarbons (see Eq. 6). The
tures and long residence times complete conversion was most striking example was that the experiment at very high
achieved. At temperatures above 240°C, all the carboxyl temperature gave very high amounts of hydrocarbons, much
groups were hydrogenated in about 3 s (see Fig. 2). The opti- higher than predicted by the model (see removed outlier in
mal temperature did not change compared to the traditional Table 2).
process; it is more dependent on the catalyst used. In contrast to the conversion, the selectivity was affected
The effect of the hydrogen pressure (ranging from 10 to 30 by the hydrogen pressure (Fig. 5). Increasing hydrogen pres-
bar, i.e., the ratio of hydrogen to FAME ranging from 60 to sure accelerates hydrocarbon formation, as can be illustrated
200 molH /molFAME) was not significant (see Fig. 3). This
2
clearly shows that the mass transfer limitations for hydrogen
were eliminated at the supercritical conditions and that the re-
action rate was controlled by kinetics. However, at very low
hydrogen concentration the model overestimated the conver-
sion (see removed outlier in Table 2). This indicates, that at
these conditions, the conversion is no longer independent of
the hydrogen pressure. Hence, at such hydrogen pressures
(the ratio of hydrogen to FAME is 20) the conversion of
FAME decreases when the hydrogen concentration is reduced
at constant temperature and residence time.
It was not possible to describe the selectivity with a model
when life time of the catalyst was included because the varia-
tions were too large (i.e., k·SEE = 17.3). Therefore, we elimi-
nated the catalyst life time as a variable from the selectivity
model and used a fixed catalyst life of 0.25 kg/kg instead (see
Table 2). FIG. 2. ConversionFAME (mol/mol%) at a hydrogen pressure of 20 bar
At severe hydrogenation conditions, i.e., at high hydrogen and life = 0.25 kgFAME/kgcatalyst, (1.5·SEE = 9.6). See Equation 5. For ab-
pressure and/or high temperature, selectivity decreased. This breviation see Figure 1.

JAOCS, Vol. 76, no. 11 (1999)

 FATTY ALCOHOL PRODUCTION AT SC-CONDITIONS 1367

FIG. 3. ConversionFAME at 250°C and life = 0.25 kgFAME/kgcatalyst, FIG. 5. SelectivityFOH at 250°C and life = 0.25 kgFAME/kgcatalyst , (k·SEE =
(1.5·SEE = 9.6). A,B = complete conversion. For abbreviation see Figure 1. 6.6). A,B = complete conversion (cf. Fig. 3). For abbreviations see Fig-
ures 1 and 4.
with points A and B, where the conversion is 100% in both
cases (Fig. 3). However, the selectivity in B, at a higher hy- ture-time combinations exists where the average yieldFOH ex-
drogen pressure, is 15% lower (Fig. 5). Thus, the “overhydro- ceeds 100% (see Fig. 6). This is due to the uncertainty in the
genation” could be minimized by reducing the hydrogen pres- model (i.e., 1.3·SEE = 6.9), and therefore yields above 107%
sure and/or temperature. imply that 100% is really achieved.
FOH yield. A maximal yield of FOH is desired, thus both By increasing the hydrogen pressure, the maximal yield of
the conversion and the selectivity should be high. A high con- alcohol is decreased. The maximum output of FOH at 30 bar
version with low selectivity results in substrate losses due to hydrogen pressure, is about 80–85% (Fig. 7). At low temper-
hydrocarbon formation. If hydrocarbons or FAME remain in atures and/or short residence times the conversion restricts
the product mixture, separation steps are required after the re- the FOH yield. By increasing either the temperature or the
actor. Commercial fatty alcohol plants operate at conversion residence time at high temperatures, the FOH fraction will
levels of 98–100% (18,19). Acceptable levels of hydrocarbon pass through an optimum and then decrease because of “over-
concentrations are below 1% in fixed-bed operation mode (19). hydrogenation,” as one can see in the contour plots of the se-
Figure 6 shows the yieldFOH at different temperatures and lectivity (see Fig. 4). The area with a high FOH yield is ex-
residence times for a fixed hydrogen pressure of 10 bar. This panding toward longer residence times and lower tempera-
contour plot can be regarded as an overlay plot of the selec- tures when the hydrogen pressure is decreased (cf. the
tivity and conversion contour plots (for example Figs. 2 and upper-left corner, Figs. 6 and 7).
4). At a hydrogen pressure of 10 bar an area with tempera- The effect of hydrogen pressure on yield can be studied
more thoroughly in a contour plot of yieldFOH against hydro-

FIG. 4. SelectivityFOH (mol/mol%) at a hydrogen pressure of 20 bar and FIG. 6. YieldFOH (mol/mol%) at a hydrogen pressure of 10 bar and life
life = 0.25 kgFAME/kgcatalyst, (k·SEE = 6.6). See Equation 6. FOH, fatty al- = 0.25 kgFAME/kgcatalyst , (1.3·SEE = 6.9). See Equation 7. For abbrevia-
cohol; for other abbreviation see Figure 1. tions see Figures 1 and 4.

JAOCS, Vol. 76, no. 11 (1999)

1368 S. VAN DEN HARK ET AL.

FIG. 7. YieldFOH at a hydrogen pressure of 30 bar and life = 0.25 FIG. 8. YieldFOH at 250°C and Life = 0.25 kgFAME/kgcatalyst, (1.3·SEE =
kgFAME/kgcatalyst , (1.3·SEE = 6.9). For abbreviations see Figures 1 and 4. 6.9). For abbreviations see Figures 1 and 4.

gen pressure and residence time at a temperature of 250°C selectivity. With FAME from rapeseed oil, the yield decreased
(Fig. 8). At short residence times the same trends as for the quickly as a result of a very short catalyst life. However, ad-
conversion can be recognized; the yieldFOH is independent of ditional experiments with methylated sunflower oil, an oil of
the hydrogen pressure used. However, at residence times high purity, could prolong the catalyst life by two orders of
above 2.5 s, the hydrogen pressure (i.e., hydrogen concentra- magnitude. This indicates that a catalyst life similar to that of
tion) clearly becomes important for achieving complete hy- operating FOH plants can be reached.
drogenation of the substrate to FOH without formation of hy- The exact cause and mechanism of the observed inactiva-
drocarbons. Only at hydrogen pressures below 20 bar was it tion are not known at present, but are being studied. Several
possible to control the selectivity and simultaneously gain full deactivation mechanisms are known. Owing to the low tem-
conversion. peratures used (compared to the melting points of the metals
Catalyst life. It is important to control the reaction condi- studied) “thermal” sintering cannot be the reason. Impurities
tions (reaction rate and selectivity) over time during a contin- in the instrumental propane did not contribute to the inactiva-
uous process. Reaction conditions are strongly related to cat- tion, as the experiments with sunflower oil indicate that a long
alyst deactivation. The catalyst deactivation can be studied catalyst life is possible. The formation of coke is yet another
using catalyst life as a variable, the fourth variable in the ex- suspected mechanism for catalyst deactivation, which needs
perimental design. In industrial processes, common catalyst to be studied. The presence of catalyst poisons, for example,
consumption is about 0.3–2.0 wt% of the produced alcohol sulfur or other contaminants in the FAME feed, might be an-
(i.e., catalyst life 50–300 kgFOH/kgcatalyst) (19). We studied other reason for the observed catalyst deactivation (20).
the process in the starting phase of the hydrogenation, at a cat- Changing the FAME source from rapeseed oil to sunflower
alyst life between 0.25–1.0 kgFOH/kgcatalyst. oil improves the catalyst life, as has been shown with our ex-
With increasing catalyst life, the maximal yield of FOH periments. Thus, the quality of the FAME feed is thus the
decreased rapidly, owing to a decrease in both conversion and most probable source for catalyst deactivation.

TABLE 3
Overview of Literature Data for the Hydrogenation of FAME to FOH in a Fixed Bed Reactora
Reaction rate LipidHSV Conditions
(mmol/gcatalyst min) (m3/m3h) Feed Bar Temperature (°C) Phases Solvent Reference
— 0.2 FAME (−) 200–300 200–250 g/l 7
0.01–0.02 0.2–0.4 FAME (C16:0/C18:0) 65 218 g/l 21
— 0.5 FAME (C12:0) 245 270 g/l 22
0.01–0.03 0.1–0.4 FAME (C16:0) 80 200-210 g/l n-Octane 9,23
0.02b 0.4 Dimethylcyclohexadicarboxylate 62 220 g 24
0.04 — FAME (C2:0) 4 (PH = 0.4) 280 g Nitrogenc 3
2
0.2 — FAME (C2:0) 40 260 g 25
0.08 2 FAME (C18:0-3) 150 (PH = 10) 240–250 sc Propane This investigation
2
a
g, vapor phase; l, liquid phase; sc, supercritical; LipidHSV, hourly space velocity based on substrate volume. For other abbreviations see Tables 1 and 2.
b
Calculated with substrate density 0.78 kg/L.
c
Nitrogen is used to maintain a constant system pressure.

JAOCS, Vol. 76, no. 11 (1999)

 FATTY ALCOHOL PRODUCTION AT SC-CONDITIONS 1369

Experimental problems. Two experiments suffered from phases are a hydrogen-rich gas phase and a FAME-rich liquid
unstable flow rates through the catalyst bed and were stopped phase resulting in a drastic decrease of the reaction rate re-
before the desired catalyst life was reached. These cases were: sulting from a reintroduction of hydrogen transport limita-
(i) very high hydrogen pressure and (ii) high hydrogen pres- tions. We have performed several screening experiments to
sure in combination with a long catalyst bed. Instead, sam- find the transition point where the single phase splits into two
ples of the same experiments at a shorter catalyst life were phases. Under the applied reaction conditions, single-phase
used in the modeling. Moreover, two of the outliers found conditions could be maintained when the substrate concentra-
during the statistical processing (Table 2) were experiments tion was increased to at least 2 mol% (=15 wt%). These re-
with a long residence time (i.e., a long catalyst bed). All these sults indicate the possibilities to increase the reactor produc-
observations may be indications of a pressure drop over the tivity by increasing the lipid concentration and reducing the
catalyst bed. The lower pressure at the end of the catalyst bed propane recycle feed.
results in reduced solubility of the oil and may cause a phase Hydrogen is an antisolvent for the substrate in the reaction
split into a heavier oil-rich phase and a gas phase, which are mixture of propane/lipid/hydrogen (see Fig. 1). Therefore, a
in equilibrium. This phenomenon and the consequences will low hydrogen pressure not only improves the selectivity but
be described in later papers. also improves the lipid solubility.
Best results and outlook. The throughput or the productiv-
ity of the reactor is an interesting parameter. The productivity
ACKNOWLEDGMENT
is often expressed as the ratio of substrate volume feed to the
reactor volume per unit of time [i.e., LHSV (m3/m3 · h−1)] or This work was financially supported by Daka a.m.b.a., Løsning,
as reaction rate (mmolFOH/gcatalyst min). When a solvent is Denmark.
used, lipid hourly space velocity (LipidHSV) instead of
LHSV is used. The LipidHSV is calculated on the FAME vol- REFERENCES
ume feed and is thus equivalent to LHSV in a traditional
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quality. Thus, the comparison in Table 3 can be considered Chemistry, Oils Fats Intl. 9:25–30 (1993).
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