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The Bioethanol-to-Ethylene
265
Printed in The Netherlands
(B.E.T.E.)
Processa
ABSTRACT
Ethanol present at low concentration in a fermentation broth which also contains some leftover
glucose as well as other fermentation residues. is totally converted into ethylene over a solid superacidic catalyst. Trifluoromethanesulfonic acid bound to the silica rich surface of the acidic
ZSM-5 zeolite is thermally stable up to 300 C and can catalyse the reaction with nearly complete
conversion at a temperature as low as 17OC. Below 2OOC, the catalyst is extremely stable even
in the presence of the high amount of water found in the feed. A rapid economical evaluation
shows that ethylene produced by the B.E.T.E. (bioethanol-to-ethylene) process has a production
cost 10% to 40% higher than petroleum ethylene. However, a more promising figure can be envisaged with a better integrated process working with cheaper raw materials.
INTRODUCTION
0166.9834/89/$03.50
PRODUCTION
Fig. 1. Comparison
material
and pretreatment;
D: cost of conversion
dration
ethylene
of ethanol
COST(%)
to ethylene
by conventional
of ethanol
catalytic
process
by B.E.T.E.
broth.
17 j.
and ethylene
hydrolysis,
process,
from biomass.
A:cost
of raw
F: cost of conversion
and dehy-
to
267
EXPERIMENTAL
Preparation
AND RESULTS
and characterization
of the catalysts
The hydrothermal synthesis of ZSM-5 zeolites and their conversion into the
acidic catalysts were reported elsewhere [ 16,171. The preparation of t.he steam
treated zeolite (first generation of B.E.T.E. cata1yst.s) and that of the superacidic ZSM-5 zeolite (latest catalyst generation) were described in some recent
patent applications [ 13-151.
(i) In particular, the st.eamed H-ZSM- 5 (Si/Al atomic ratio = 21) in powder
form, was obtained by stream treating at 500C for 3 h prior to its extrusion
with bentonite [ 131.*Al magic angle sample spinning NMR (Al-MASS
NMR) of such a treated powder did not show any significant presence of the
octahedral aluminium; thus, the existence of a new aluminium species assumed
to be the pentacoordinated aluminium was suggested [ 18,191. Moreover, the
hydrothermal treatment of the ZSM-5 zeolite seems to significantly affect the
overall acidity, as shown by our latest ammonia TPD studies [ 201.
(ii) One way of preparing superacidic zeolites is to coat the silica rich surface
of ZSM-5 zeolite (acid form) with triflic acid (trifluoromethanesulfonic acid
or TFA). The incorporation of triflic acid onto the H-ZSM-5 (powder) is done
by slowly adding a solution of TFA dissolved in a minimal amount of solvent
(acetone, for instance) with gentle stirring. The mixture is allowed to air dry
at room temperature for several hours with periodic mixing. The solid obtained
is then heated at 120 C for (at least ) 12 h [ 141. The final catalyst was prepared
by extrusion in the presence of bentonite as binder [ 171.
The resulting material (H-ZSM$/TFA,
powder) is stable up to 300C
whereas pure triflic acid starts boiling at 162C. In fact, thermal gravimetric
analysis shows a loss of weight starting at 300 C which corresponds exactly to
the amount of TFA incorporated into the ZSM-5 zeolite (see Fig. 2). Moreover,
the volume of n-hexane adsorbed into the TFA treated zeolite decreased with
the increase of TFA loading, suggesting a certain pore size narrowing due to
the presence of TFA on the zeolite pore walls (Table 1).
The adsorption of n-hexane and water was done following the procedure
described by Le Van Mao [ 211 and Le Van Mao et al. [ 221.
Solid state *Si-MASS NMR of this material (spectra recorded on a Varian
XR-300 spectrometer at 59.59 MHz) shows some deshielding effects of the
bonding between the TFA and the surface silicon atoms of the ZSM-5 zeolite.
Pure H-ZSM-5 zeolite shows two bands (chemical shifts 6= - 112 ppm and
6= - 107 ppm, with respect to tetramethylsilane) which are attributed to the
Si(-0-Si),
and Si(-O-Al) (-0-Si), bonding, respectively. Spectra of H-ZSM5/TFA samples have an additional band (shoulder) at 6= - 116 ppm; their
- 107 ppm band have a significantly lower intensity.
Although the - 116 ppm band is not strictly peculiar for the H-ZSM-5/TFA
268
400
300
200
temperatre
500
[c)
Fig. 2. Thermal gravimetric analysis of pure (A j ZSM-5 and (B) ZSM-5 with TFA coated on
surface (TFA loading: 4 wt.-%).
TABLE 1
Variations in the adsorption properties of the H-ZSM-5 zeolite (silicon-to-aluminium
the TFA loading.
TFA loading
(wt.-%)
n-Hexane adsorbed
(vol.-%)
Water adsorbed
iv01 %)
0
1.1
3.3
5.3
1.2
9.3
6.8
5.9
6.0
4.3
10.5
9.0
10.8
9.9
12.4
10) with
zeolite (titanium-silicalite TS-1 [ 231, for instance, shows the same band), these
NMR spectra can provide useful indications for further investigation on the
modified zeolite surface.
Catalytic testing and analysis of the reaction products
The fermentation broth from which the yeast has been removed, was sent
directly to a special vaporiser. The latter was set at 120-150C to vaporize the
volatile compounds without decomposing the leftover glucose and the yeast
nutrient - which can then be recycled to the fermentor or periodically removed
as valuable by-products such as fodder. The gaseous mixture which consisted
of ethanol, steam and some other volatile substances coming from the previous
steps, flowed through a preheating zone to the catalyst bed, as shown in Fig. 3.
269
catalyst
bed
=l.(..Io180t
preheating
outlet
for
zone
non-volatile
i
J
substances
-ethylene
60.9 wt.-%
+ water
39.1 wt.-%
Table 3 reports the catalytic data of the H-ZSM-5 zeolites treated with 2 wt.% of triflic acid. The influence of the reaction temperature, the W.H.S.V., and
the silicon-to-aluminium atomic ratio of the zeolite catalyst, on the ethylene
yield can be particularly emphasized.
(92% Al 0)
(Stem Chem)
Silicalite
(Union Garb.)
H-Y (Linde)/TFA
Nafion NR-50
(Aldrich, Beads)
H-ZSM-5
H-ZSM-5
(steamed)
H -ZSM-,5
Alumina, Acidic
(Stem Chem)
;I-Alumina/TFA
2
2.0
2
-
_
-
10
-
> 100
21
21
200
200
200
200
200
200
400
400
Temp
(Cl
TFA
loading
(wt.-%)
Catalyst
Si/Al
ratio
Reaction
catalyst
TABLE 2
1.0
1.0
1.0
1.0
1.0
1.0
3.2
3.2
WHSV
(h-l)
conditions
10
10
10
10
10
10
15
15
Feed
ethanol
(vol.-%)
43.4
12.0
13.7
0.0
14.0
0.0
96
98
(wt.-%)
Conversion
99.6
99.8
93.8
100.0
49
99
Ethylene
Product
(% )
5.3
0.0
0.4
0.2
28
1
Other light
olefins
selectivity
0.9
0.0
0.0
0.0
_-
23
0
--
Other hydrocarbons
271
,
O, ethylene
0
yield
triflic
acid5
0
0
yield
Fig. 4 reports the effects of the triflic acid loading on the ethylene yield at
two reaction temperatures (185 C and 170aC ) .
DISCUSSION
A high ethylene production can be obtained with catalysts of the first generation (hydrothermally treated H-ZSM-5 zeolites). However, the required
reaction temperatures are so high (at least 300 C ) that these catalysts undergo
a slow but definite activity decay under the joint effects of heat and steam
(water from the feed). This decay results in a decrease in acid density which
stems from both the annealing effects on hydroxyl groups [24,25] and the
removal of framework aluminium atoms, the latter occurring mainly under
more severe hydrothermal conditions ]26].
Although to our knowledge no strong experimental evidence has been found
for the way in which the triflic acid is bound to the zeolite surface, results from
thermal analysis and Si-MASS-NMR seem to suggest that triflic acid is not
merely dissociatively adsorbed onto the zeolite surface (Fig. 5, Cl ) but that it
actually reacts with the zeolite hydroxyl group to yield the surface species as
tentatively described in Fig. 5, C2. The probability of having such a species is
supported by previous works on reaction of TFA over silicon and tin compounds [ 271. Furthermore, Tanabe and Hattori (281 have hypothesized a similar situation (Fig. 5, A) where SbF, is allowed to react on silica-alumina
support.
Therefore, there is a clear cooperative effect between the zeolite surface acid
sites and the superacidic centres created by the triflic acid, and this leads to a
tremendous enhancement in the yield of ethylene. The hypothesized superacidic centers (Fig. 5, C2) also reflect the positive influence of the zeolite.
Aluminium atoms content on the cataiytic activity (the lower the silicon-toaluminium atomic ratio of the ZSM-5 zeolite, the higher the ethylene yield of
272
(+,I
i
O\
A/4
/a
/-
/O
bYi\
PISi
lo\
/O
/,.F\ /*\*/
-
p
\
surface bonding;
modified
TABLE 3
Catalytic data for the H-ZSM-5 zeolites treated with TFA (2 wt.-%)
Feed is 10 wt.-% ethanol in water
Catalyst
Si/
Al
Temp.
WHSV
Conversion
(Cl
(h-)
to hydroc.
H-ZSM-5/TFA
10
H-ZSM-5/TFA
21
54
Butenes
Others
205
0.9
99.2
95.6
1.3
205
2.4
4.5
98.2
99.0
0.3
2.6
0.7
0.5
_
90.0
99.7
0.1
0.2
1.1
97.3
99.9
0.1
190
0.9
94.8
99.1
0.3
0.5
185
1.0
77.3
99.8
0.1
0.1
180
1.1
73.9
99.2
0.3
170
1.0
41.9
99.1
0.6
0.4
0.3
200
1.0
95.8
97.7
1.1
0.9
0.3
285
1.0
73.7
99.3
0.3
0.3
0.1
200
1.0
72.0
98.1
0.4
1.5
205
200
H-ZSM-5/TFA
Propylene
the catalyst, see Table 3)) as well as a high resistance to the leaching action of
steam at temperatures well above the boiling point of TFA.
Other indirect experimental evidence of such a cooperative action is found
273
274
cause the system is approaching the 300C the unstability temperature for
bound TFA.
The equipment required for the B.E.T.E. conversion is very simple (atmospheric pressure, temperature: 170-185 C ). No corrosion problems are envisaged at present. The vaporiser design allows in principle the recycling of excess
glucose and yeast nutrients, and thus, this will provide some flexibility to the
previous alcoholic fermentation step.
The net energy requirement (calculated in basis of the thermodynamic and
kinetic data from ref. 18) is only 20% of that usually calculated for the conventional two-stage distillation of ethanol (see Table 4 and ref. 10).
Table 5 shows a very approximate estimate of the ethylene production cost
with the B.E.T.E. process, as well as some values for the production cost of
petroleum ethylene.
The value of ethanol is U.S.$O.25 per liter for production from fermentation.
This assumption reflects and corrects (in consideration of the todays technology [ 61) the value proposed by the New Zealand Forest Research Institute.
The latter agency in 1979 gave a figure of less than U.S.$ 0.20 per liter of
ethanol, according to the data they had obtained from a pilot plant (a twostage Madison percolation process for the hydrolytic step, starting from wood
materials) [ 32,331.
As a result of our estimates, the production cost of 1 lb of bio-ethylene is
TABLE 4
Net process energy requirement for some processes of ethanol recovery or conversion
Process
lo6 J/l
27 400
7.6
19 200
5.4
21000
5.9
1800
0.5
5 500
1.5
275
TABLE 5
Production cost estimates (April 1988, in U.S. dollars)
Rio-ethylene (ethylene from the B.E.T.E. process)
.
Raw material: wood
.
Production cost (assumed of fermentation ethanol:
$0.25/l (or Can. $0.31/l)
.
Production cost of unpurified fermentation broth which
contains 11 of recoverable ethanol (R.E. ) :
$0.21 (85% of $0.25)
.
B.E.T.E. process cost: 5% or $0.01/l of R.E.
.
11 of R.E. provides 1.05 (0.48 kg) of ethylene
.
Credit for by-products (fodder, etc.) and yeast nutrients recycling: 20%
.
Final production cost of ethylene: $O.l7/lb or $0.375/kg
Petro-ethylene (ethylene from petroleum or natural gas derivatives feedstocks)
.
Current selling prices (April 1988):
highest: $0.24/lb or $0.53/kg
lowest: $O.l7/lb or $0.375/kg
.
Estimated production cost (with by-product credit):
highest: $O.l6/lb or $0.35/kg
lowest: $ O.ll/lb or 8 0.24/kg
circa $0.17 ($0.375 per kg) whereas that of 1 lb of petro-ethylene ranges from
$0.11 to 0.16 (from $0.24 to $0.35 per kg) (such a large range is due to several
factors: location of processing plants, cost and nature of petroleum feedstocks,
etc.). The selling price of ethylene ranges from $0.17 and 0.24 per lb (from $
0.375 to $0.53/kg) [34].
Thus the difference ranges from 10% to 40%. However, this is not the least
discouraging because of the following factors:
- Ethylene demand and price continue to increase.
- Ethylene production cost in some countries is increasing as the steam-cracking process (actual major source of ethylene) is shifting to heavier petroleum
feedstocks.
- Substantial progress is expected in the hydrolytic step within the entire process from biomass or cellulosic materials. The B.E.T.E. reaction can accommodate any ethanol content in the fermentation broth ranging from 2 to 19
vol.-%, thus, providing a high flexibility to the fully integrated process biomass-to-ethylene. New superacidic catalysts are in the development stage for
converting by-products (carboxylic acids, furfural derivatives, etc.) [31] into
more commercially valuable chemicals and will contribute to increasing the
by-product credit of the process.
- Renewable biomass is available in some countries at very low cost.
- Several countries with no petroleum or natural gas resources, are ready to
276
Triflic acid which boils at 162C can react with the hydroxyl groups of the
ZSM-5 zeolite. The resulting surface species is thermally stable up to 300C.
Such a surface modification provides a higher acidity and an enhanced shapeselectivity for the selective conversion of aqueous ethanol into practically pure
ethylene. The reaction is carried out at 200C or less, and there is practically
no need for prepurification or predistillation of the fermentation broth. Further, ethanol content as low as 2 vol.-% can be used in the B.E.T.E. process,
this would be advantageous for any process of biomass conversion using dilute
acid in the hydrolysis step.
ACKNOWLEDGEMENTS
REFERENCES
1
2
3
4
5
6
7
8
9
10
11
12
13
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