Transformation of Bio-Oil Into BTX by Bio-Oil Catalytic Cracking
Transformation of Bio-Oil Into BTX by Bio-Oil Catalytic Cracking
Transformation of Bio-Oil Into BTX by Bio-Oil Catalytic Cracking
ARTICLE
Transformation of Bio-oil into BTX by Bio-oil Catalytic Cracking
Jiu-fang Zhu, Ji-cong Wang, Quan-xin Li ∗
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
Production of benzene, toluene and xylenes (BTX) from bio-oil can provide basic feedstocks
for the petrochemical industry. Catalytic conversion of bio-oil into BTX was performed by
using different pore characteristics zeolites (HZSM-5, HY-zeolite, and MCM-41). Based on
the yield and selectivity of BTX, the production of aromatics decreases in the following
order: HZSM-5>MCM-41>HY-zeolite. The highest BTX yield from bio-oil using HZSM-5
reached 33.1% with aromatics selectivity of 86.4%. The reaction conditions and catalyst
characterization were investigated in detail to make clear the optimal operating parameters
and the relation between the catalyst structure and the production of BTX.
Key words: Bio-oil, BTX, Catalytic cracking
∗ Author to whom correspondence should be addressed. E-mail: Bio-oil was produced by the fast pyrolysis of biomass
liqx@ustc.edu.cn in a circulating fluidized bed with a capacity of 120 kg/h
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478 Chin. J. Chem. Phys., Vol. 26, No. 4 Jiu-fang Zhu et al.
TABLE I Main organic compounds (ethyl acetate extraction) in the bio-oil. tGC in min and x is the content of an organic
compound.
tGC Formula Compounds x/%
6.16 C4 H8 O2 2-Butanone, 4-hydroxy 0.11
6.62 C7 H8 O2 (2-Oxo-3-cyclopenten-1-yl)acetaldehyde 5.20
7.85 C5 H8 O3 2-Oxopropyl acetate 2.44
12.33 C6 H6 O Phenol 5.75
13.75 C6 H8 O2 Methyl cyclopentenolone 6.89
16.00 C7 H8 O2 Mequinol 9.40
19.16 C10 O8 Naphthalene 0.89
19.65 C8 H10 O2 2-Methoxy-6-methyl phenol 5.60
20.97 C12 H24 O3 3-Hydroxy dodecanonic acid 3.33
27.01 C25 H32 O8 6,7-Epoxypregn-4-ene-9,11,18-triol-3,20-dione-11,18-diacetate 4.62
29.35 C39 H78 O3 3-Octadecoxypropyl octadecanoate 1.28
31.35 C18 H32 O16 a-Maltotriose 0.99
34.33 C30 H42 O10 Sarreroside 1.87
37.58 C14 H10 Phenanthrene 0.29
38.50 C25 H36 O5 12-Acetyloxy-20-oxopregn-16-en-3-yl-acetate 0.18
41.22 C18 H24 O 17-Desoxyestradiol 1.56
43.12 C25 H26 O5 (3-Acetyloxy-4,4,10,13-tetramethyl-7-oxo-2,3,8,9,11,12,14,15,16,17-decahydro-1H- 1.11
cyclopenta[a]phenanthren-17-yl) acetate
44.63 C27 H42 O4 2-(3-Acetyloxy-4,4,10,13,14-pentamethyl-2,3,5,6,7,11,12,15,16,17-decahydro-1H- 0.81
cyclopenta[a]phenanthren-17-yl)propanoic acid
45.42 C41 H64 O13 Digitoxin 0.14
oil at our Lab [24−28]. The density of bio-oil is flushed with He at 120 ◦ C for 1 h, the programmed-
1.160 Mg/m3 , LHV is 17.77 MJ/kg, and pH is 3.3. And desorption of NH3 was run from 120 ◦ C to 700 ◦ C with a
the main organic compounds (ethyl acetate extraction) heating rate of 10 ◦ C/min. The desorbed ammonia was
in the bio-oil are shown in Table I. The main elemental measured by a gas chromatograph (GC-SP6890, Shan-
composition of bio-oil feedstock derived from fast py- dong Lunan Ruihong Chemical Instrument Co., Ltd.,
rolysis of straw stalk contains 46.1%C, 7.1%H, 1.6%N, Tengzhou China) with a thermal conductivity detector
45.2%O, and 0.07%ash. Water content in the crude bio- (TCD). The N2 adsorption/desorption isotherms of the
oil is about 40.2%. The chemical formula of the oxy- catalysts were measured at 196 ◦ C using the COULTER
genated organic compounds of the crude bio-oil feed can SA 3100 analyzer.
be expressed as CH1.85 O0.74 .
DOI:10.1063/1674-0068/26/04/477-483 c
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Chin. J. Chem. Phys., Vol. 26, No. 4 Bio-oil into BTX by the Bio-oil Catalytic Cracking 479
DOI:10.1063/1674-0068/26/04/477-483 c
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480 Chin. J. Chem. Phys., Vol. 26, No. 4 Jiu-fang Zhu et al.
which were obviously higher than the levels using HY- The products observed were divided into the fol-
zeolite or MCM-41 catalyst. On the other hand, the lowing categories: liquid organic compounds (mainly
coke yields using HZSM-5, MCM-41 and HY-zeolite are BTX), gaseous products (CO, CO2 , CH4 , C2-C4 alka-
about 23.8%, 20.5%, and 33.3%, respectively (reaction nes and C2= -C4= olefins) and coke (Table IV). At
condition: T =500 ◦ C, f (N2 )=200 cm3 /min, reaction higher reaction temperature (>500 ◦ C), the liquid or-
time=0.5 h). The transformation of the bio-oil over ganic products primarily consist of benzene, toluene
the Y-types zeolite produced more coke than that us- and xylenes (BTX), which are expected to mainly
ing HZSM-5, leading to a decrease in the BTX yield. result from the deoxygenation of oxygenated organic
Table III summarizes the main characteristics of the compounds along with the removal of groups such as
catalysts used in this work. The different performance methyl, hydroxyl and methoxy groups in the aromatic
of the transformation of the bio-oil into BTX using dif- rings with the zeolite catalyst. The bio-oil contained
ferent zeolite catalysts should be mainly attributed to acids, alcohols, aldehydes, ketones, levoglucosan and
the differences in pore topology and acidities. esters, these compounds were almost completely con-
verted to the hydrocarbons (such as BTX) through de-
oxygenation, cracking and aromatization reactions at
the reaction temperature of 550 ◦ C. Increasing the tem-
B. Effect of temperature on transformation crude bio-oil
perature from 500 ◦ C to 600 ◦ C, the carbon yield of
BTX slightly decreased from 30.4% to 26.8l% due to
Table IV shows the effect of temperature on the cat-
the secondary cracking of the aromatic hydrocarbons.
alytic transformation of the bio-oil with the selected
The selectivity of BTX reaches a highest value of about
HZSM-5 catalyst. The overall carbon yields of liquid
86.3% at 600 ◦ C. The overall by-products like phenols,
organic products decreased with increasing the reac-
ethylbenzene, naphthalenes and indenes were reduced
tion temperature. A higher temperature will lead to
with increasing the reaction temperature. The above re-
the second cracking of liquid organics and the forma-
sults show that the BTX yield decreased with increasing
tion of gas hydrocarbons such as gaseous alkanes and
the reaction temperature, causing by the gasification of
olefins. Based on the component analysis, the bio-oil
bio-oil at high temperature. However, when the tem-
fed consisted of a complex mixture of oxygenated or-
perature was lower than 500 ◦ C, the bio-oil conversion
ganic compounds mainly including acids, ketones, al-
decreased, leading to the decrease in the production of
cohols, aldehydes, esters, substituted phenols together
BTX.
with levoglucosan, aromatic oligomers and other oxy-
genates (Table I). It should be pointed out that a large On the other hand, the distribution of the aro-
amount of oxygen (45.2%) is contained in the bio-oil. matics derived from the catalytic cracking of the
Catalytic conversion of these oxygenated organic com- bio-oil was also sensitive to the operation temper-
pounds in the bio-oil over a zeolite catalyst generally in- ature (Table IV). The order of different aromatics
volves complex reactions, mainly including deoxygena- (based on carbon yield) obtained at 500 ◦ C is as fol-
tion (decarbonylation, decarboxylation, dehydration), lows: toluene>benzene>xylenes>ethylbenzene>C9+
cracking, hydrogen transfer, cyclization, aromatization aromatics>phenols. With increasing reaction tempera-
and oligomerization reactions. The above observation ture, the formation of benzene and toluene significantly
suggests an increasing impact on the transformation of increased, accompanied by an obvious decrease in C9+
oxygenates into hydrocarbons at higher temperature. aromatics, phenols and xylenes. These changes in the
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Chin. J. Chem. Phys., Vol. 26, No. 4 Bio-oil into BTX by the Bio-oil Catalytic Cracking 481
FIG. 1 Catalyst stability in the catalytic cracking of bio-oil. Aromatics carbon yield (a) and aromatics selectivity (b) over
HZSM-5 catalyst, respectively. Reaction conditions: T =500 ◦ C, WHSV=2.0 h−1 .
aromatics distribution suggests that higher temperature quently, followed by the secondary reactions to produce
is favorable for further removal of groups from the ini- gas hydrocarbons through deoxygenation, cracking and
tial heavier aromatics (for example demethylation of hydrogen transfer processes.
xylenes), resulting in the increase in the benzene and
toluene yields.
Moreover, the gas products mainly consisted of CO, C. Effect of WHSV on the transformation of crude bio-oil
CO2 , C1-C4 alkanes and C2= -C4= olefins, and in-
creased with the temperature increasing from 500 ◦ C Table V shows the production of BTX from the cat-
to 600 ◦ C. CO and CO2 are formed via the decar- alytic cracking of bio-oil as a function of weight hourly
bonylation and decarboxylation reactions of the oxygen- space velocity (WHSV). WHSV is defined as the mass
containing organics over the zeolite catalyst. For the flow rate of the feed divided by the mass of the cata-
gaseous alkanes and light olefins, the oxygenated organ- lyst in the reactor. With the increase of WHSV from
ics in the bio-oil can be directly cracked to these smaller 1 h−1 to 6 h−1 , the BTX carbon yield gradually reduced
hydrocarbons through the deoxygenation and cracking from 33.1% to 30.7%. Increasing WHSV also resulted
processes i.e., in the decrease in the BTX selectivity, accompanied by
Cx Hy Oz → Cn H2n (n = 2 − 4) + an increase in the hydrocarbons selectivity of ethylben-
zene and phenol. Especially, the formation of benzene
Cn H2n+2 (n = 1 − 4) + H2 O/CO/CO2 (4)
decreased with the increasing WHSV, accompanied by
Also, the larger molecules in the bio-oil may be cat- the increase in the production of toluene and xylenes.
alytically cracked to the lighter organics, and subse- In addition, the gaseous alkanes and light olefins were
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482 Chin. J. Chem. Phys., Vol. 26, No. 4 Jiu-fang Zhu et al.
FIG. 2 XRD spectra for the fresh HZSM-5 catalyst and the
used HZSM-5 catalyst after catalytic conversion of bio-oil at
T =500 ◦ C and WHSV=2.0 h−1 .
IV. CONCLUSION
E. Catalyst characterization
Catalytic pyrolysis of bio-oil for the production of
Figure 2 shows the XRD spectra for the pristine and BTX was performed by different pore characteristics
the used catalysts of HZSM-5. The structure of the zeolites. The highest BTX yield from bio-oil using
HZSM-5 zeolite remained after operating the cracking HZSM-5 reached 33.1% with aromatics selectivity of
of the bio-oil. However, the XRD peak intensity for 86.4%. The reaction parameters and the types of molec-
the used catalyst was reduced as compared with the ular sieve catalysts have an important impact both on
fresh one, indicating that the crystallinity decreased the BTX yield and its selectivity. Production of BTX
during the bio-oil cracking process. Figure 3 presents are expected to mainly result from the deoxygenation,
the NH3 -TPD profiles for the fresh and used HZSM-5 cracking and aromatization reactions of oxygenated or-
catalysts. All tested catalysts showed three acid sites ganic compounds in the bio-oil. The conversion of
with different acid strength. One strong profile around bio-oil to BTX may potentially provide an alternative
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Chin. J. Chem. Phys., Vol. 26, No. 4 Bio-oil into BTX by the Bio-oil Catalytic Cracking 483
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