US 20090227823Al

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2009/0227823 A1
Huber et al. (43) Pub. Date: Sep. 10, 2009

(54) CATALYTIC PYROLYSIS OF SOLID Publication Classi?cation

BIOMASS AND RELATED BIOFUELS,
(51) Int. C1.
AROMATIC, AND OLEFIN COMPOUNDS 0070 1/00 (2006.01)
(52) us. c1. ....................................... .. 585/324; 585/310
(75) Inventors: George W. Huber, Amherst, MA
(US); Yu-Ting Cheng, Amherst, (57) ABSTRACT
MA (US); Torren Carlson, Hadley, This invention relates to compositions and methods for ?uid
MA (US); Tushar Vispute, hydrocarbon product, and more speci?cally, to compositions
Amherst, MA (US); Jungho Jae, and methods for ?uid hydrocarbon product via catalytic
Amherst, MA (US); Geoff pyrolysis. Some embodiments relate to methods for the pro
Tompsett, ShreWsbury, MA (US) duction of speci?c aromatic products (e.g., benzene, toluene,
naphthalene, xylene, etc.) via catalytic pyrolysis. Some such
Correspondence Address: methods may involve the use of a composition comprising a
WOLF GREENFIELD & SACKS, RC. mixture of a solid hydrocarbonaceous material and a hetero
600 ATLANTIC AVENUE geneous pyrolytic catalyst component. In some embodi
BOSTON, MA 02210-2206 (US) ments, the mixture may be pyrolyZed at high temperatures
(e.g., between 5000 C. and 10000 C.). The pyrolysis may be
(73) Assignee: University of Massachusetts, conducted for an amount of time at least partially suf?cient
Boston, MA (US) for production of discrete, identi?able biofuel compounds.
Some embodiments involve heating the mixture of catalyst
(21) Appl. No.: 12/397,303 and hydrocarbonaceous material at high rates (e.g., from
about 500 C. per second to about 10000 C. per second). The
methods described herein may also involve the use of spe
(22) Filed: Mar. 3, 2009
cialiZed catalysts. For example, in some cases, Zeolite cata
Related US. Application Data
lysts may be used; optionally, the catalysts used herein may
have high silica to alumina molar ratios. In some instances,
(60) Provisional application No. 61/068,001, ?led on Mar. the composition fed to the pyrolysis reactor may have a rela
4, 2008, provisional application No. 61/098,284, ?led tively high catalyst to hydrocarbonaceous material mass ratio
on Sep. 19, 2008. (e.g., from about 5:1 to about 20:1).
Patent Application Publication Sep. 10, 2009 Sheet 1 0f 19 US 2009/0227823 A1

26

%
74

_
-
_
.

48753 0-.. u
.

_7
_7
O_
0_
E23 .i"
_.
O
8.

67
m43
3%
n
n
. u m _
- u _ n

"o0 3
,
.5

1
|Ila||
1u
_5 O
8

4_Ln
1_
1_
hil?Im.i
2
.Y

IA_. 6_
_
a
n
s
Q
4

a4
=2

4O4

4
u
24

FIG. 1
Patent Application Publication Sep. 10, 2009 Sheet 2 0f 19 US 2009/0227823 A1

A.I
5O

E3c5 0 4321.0 Xylitol vGlucose Cellobiose Cellulose

FIG. 2A

b 507 (a) = glucose feed

45 (b) = cellulose feed
40 (0) = cellobiose feed
(d) = xylitol feed
35
30"

atl53 21.1.
50 .
_
_,

Tol. E-Ben. m.e-Ben. Ind.

V Xyl. tm~Ben.
Aromatic Species _

FIG. 2B
Patent Application Publication Sep. 10, 2009 Sheet 3 0f 19 US 2009/0227823 A1

O . r . {Um . . .. , .3. K 11 ._. . m.

1. 1'0 100 1000

Nominal heating rate I "C s'71 -_-.
FIG. 3
Patent Application Publication Sep. 10, 2009 Sheet 4 0f 19 US 2009/0227823 A1

@050

YC(aire%blod)n
0 5 1O 15 20
Catalyst to Glucose Ratio-m.
FIG. 4A

catalyst to glucose ratios

' _ ti (a) = 9

(c) = 2.3
I 40 ' (d)= 1.5
(b)@
@30
E
IE 10 - 1* 1? I

g .
__

Fur. Furf. M-Fur. 4-M- Fur-2

, Furf MeOH
oxygenated specles --->
FIG. 4B
Patent Application Publication Sep. 10, 2009 Sheet 5 0f 19 US 2009/0227823 A1

ZSM~5 Silicalite B~ze1oIite Silica- Y-zeolite

alumina
FIG. 5
Patent Application Publication Sep. 10, 2009 Sheet 6 0f 19 US / 1

B
mwA

.m
m
C
C
n
.nluM
C
nw.
OM
w SO
7
m
82

m
0E
I

421761D5
i5Q525.> 0O .
_
_
_

FIG. 6A
Patent Application Publication Sep. 10, 2009 Sheet 7 0f 19 US 2009/0227823 A1

(a) = 23
(b) = 30
(c) = 55
(d) = 80
A

5Q
i:- I SiO2/Al203=23
'r'
5 I SiO2/Al203=3O
Q
i; I SiO2/Al203=55
w I SiO2/Al203=8O

Ben. T01. E-Ben. M,E-Ben. Ind. Nap.

Xy]. Tm-Ben.

FIG. 6B
Patent Application Publication Sep. 10, 2009 Sheet 8 0f 19 US 2009/0227823 A1

56

74

48

22 46

FIG. 7
Patent Application Publication Sep. 10, 2009 Sheet 9 0f 19 US 2009/0227823 A1

C(Yairebl7o0n)

Glucose Wood Sugarcane Sugarcane Sugarcane Corn Slover

(Sao Paulo) (LeandroBrazil) (PuuneneJ-ID

I Aromatics 12 CO2 I CO I Coke

FIG. 8A
Patent Application Publication Sep. 10, 2009 Sheet 10 0f 19 US 2009/0227823 A1

E1 Glucose I Wood I Sugarcane I Sugarcans I Sugzrcanc I Com Shaver

(Sao Paulo) (LeandroBrazil) (Puunenslil)

i, 45
3;- 40
IE 35
3 so
= 20
g 15
5

Ben. T01. E Ben. ME-Ben.

XyL "?n-Ben.

FIG. 8B
Patent Application Publication Sep. 10, 2009 Sheet 11 0f 19 US 2009/0227823 A1

140 u 18

120 _ 16

g A
'2 14 c
_<_; 100 Cellulose '2
13 (pvroprobe) -- 12 2
5 so - _ g
7 Wood Cellulos|c __ 10 E
5 (pyroprobe) Ethanol _-> _\,
_ o .
E 60 - 100 /> yleld __ 8 g
g 3
0- _ 6 a
Z 40 - c
H m
D -- 4
O
20 - n 2

0 I l l | | | I I I 0

O 10 20 30 4O 50 6O 70 80 90 100
Theoretical Yield (%)
FIG. 9
Patent Application Publication Sep. 10, 2009 Sheet 12 0f 19 US 2009/0227823 A1

80 -

NO l

coke
O) Q 1

aromatics

(JCaYr%bio)neld Q /

2o
10 A A CO2 A A

400 500 600 700 ' 800

Temperature (deg C)
FIG. 10
Patent Application Publication Sep. 10, 2009 Sheet 13 0f 19 US 2009/0227823 A1

45
40
35 _ aromatics

30

C(Yaire%blod)n 25
2O
15
10
002

l l l l l

46 68 90 112 134 156

Si/Al molar ratio

FIG. 11
Patent Application Publication Sep. 10, 2009 Sheet 14 0f 19 US 2009/0227823 A1

30.0

25.0 i

(yCair%beol)nd I Ole?ns
I Aromatics
f5 Q
6

0.0 ~

0.35 0.89 2.79

FIG. 12
Patent Application Publication Sep. 10, 2009 Sheet 15 0f 19 US 2009/0227823 A1

40.0 -

35.0
I ?xed bed
I Pywpwbc
30.0

(ycair%beol)nd M Pc

ES

10.0
Patent Application Publication Sep. 10, 2009 Sheet 16 of 19 US 2009/0227823 A1

Condensers

Biomass
Patent Application Publication Sep. 10, 2009 Sheet 17 0f 19 US 2009/0227823 A1

01 1

A 1

(YCaire%blod)n U)[\J

0 I - I I l
Ben. Tol. Xyl. Nap. Eth. Pro.

FIG. 15
Patent Application Publication Sep. 10, 2009 Sheet 18 0f 19 US 2009/0227823 A1

14
E Olefins
I Aromatics

(YCaire%blodn) m

0.07 1.00
Biomass Space Velocity (hr'1)
FIG. 16A

m C)
[ii Ole?ns
I Aromatics
O) O |

(SCealr%cbtiov)ny o) C)
S
8 1

0.07 1.00
Biomass Space Velocity (hr'1)
FIG. 16B
Patent Application Publication Sep. 10, 2009 Sheet 19 0f 19 US 2009/0227823 A1

Norman Radii
Zeolite. IAdjusted Pore Size (A)
MGM-22 6.2
ZSM-23 5 .9
ZSM-57 6.1
Ferrierite 6.1
SUZ-4 5 .9
EU-l 6.1
ZSM-l 1 6.1
(S)A]PO-31 6.1
882-23 6
FIG. 17