US008153027B2

(12) United States Patent (10) Patent No.: US 8,153,027 B2

Klepper et al. (45) Date of Patent: Apr. 10, 2012
(54) METHODS FOR PRODUCING SYNGAS 4.675,344 A 6/1987 Conway et al.
4,699.632 A * 10/1987 Babu et al. .................. 48.197 R
4,749,724 A 6/1988 Quarderer et al.
(75) Inventors: Robert E. Klepper, Arvada, CO (US); 4,752,622 A 6, 1988 Stevens
Arie Geertsema, Westminster, CO (US); 4,752,623 A 6, 1988 Stevens
Shakeel H. Tirmizi, Matawa, NJ (US); 4,762,858 A 8, 1988 Hucul et al.
4,775,696 A 10, 1988 Prada-Silva et al.
Franch M. Ferraro, Westminster, CO 4,824,869 A 4, 1989 Prada-Silva et al.
(US) 4,825,013 A 4/1989 Quarderer et al.
4,886,772 A 12/1989 Prada-Silva et al.
(73) Assignee: Range Fuels, Inc., Denver, CO (US) 4,980,380 A 12/1990 Wong et al.
4,999,133 A 3/1991 Banquy et al.
(*) Notice: Subject to any disclaimer, the term of this 5,451,558 A
RE35,377 E
9/1995 Campbell et al.
1 1/1996 Steinberg et al.
patent is extended or adjusted under 35
U.S.C. 154(b) by 130 days. (Continued)
(21) Appl. No.: 12/166,167 FOREIGN PATENT DOCUMENTS
EP 1860O88 11, 2007
(22) Filed: Jul. 1, 2008 (Continued)
(65) Prior Publication Data OTHER PUBLICATIONS
US 2009/OO18222 A1 Jan. 15, 2009 Division of Chemical Reaction Engineering, KTH Kungl.
Tekniska Högskolan, “Torrefied Wood an Alternative to Charcoal for
Related U.S. Application Data Reducing Deforestation'. http://hem.fyristorg.com/Zanzi?torrefac
(60) Provisional application No. 60/948,653, filed on Jul.9, tion.html, Feb. 2001.
2007. (Continued)
(51) Int. Cl. Primary Examiner — Wayne Langel
COIB 3/22 (2006.01) (74) Attorney, Agent, or Firm — O'Connor & Company;
(52) U.S. Cl. ....................................................... 252/373 Ryan P. O'Connor
(58) Field of Classification Search ................... 252/373
See application file for complete search history. (57) ABSTRACT
(56) References Cited
This invention features methods and apparatus for producing
syngas from any carbon-containing feed material. In some
U.S. PATENT DOCUMENTS embodiments, a Substoichiometric amount of oxygen is used
to enhance the formation of syngas. In various embodiments,
4,592,762 A * 6/1986 Babu et al. .................. 48.197 R both oxygen and steam are added during the conversion of the
4,607,055 A 8, 1986 Grazioso et al.
4,607.056 A 8, 1986 Grazioso et al. feed material into syngas. The Syngas can be converted to
4,616,040 A 10, 1986 Grazioso et al. alcohols, such as ethanol, or to other products.
4,628,113 A 12/1986 Current
4,661.525 A 4, 1987 Grazioso et al. 19 Claims, 9 Drawing Sheets

Devolatilization 201 Reforer 301

To Quench.
Compressor

510 O2 + Steam injection

900 Eductor
Drive Gas
Steam

t 520 Ash-Quench/Slag
Removal System
 US 8,153,027 B2
Page 2

U.S. PATENT DOCUMENTS 7,091,251 B2 8, 2006 Guillard et al.

5.990,039 A 11, 1999 Paul et al. 7,144.923 B2 12/2006 Fitzpatrick
A 10, 2000 Lightner 7,169,821 B2 1/2007 Branson
6,133,328 7,176, 160 B2 2/2007 Espinoza et al.
6,156,693 A 12, 2000 Song et al. 7,192,987 B2 3/2007 VanEgmond et al.
RE37,046 E 2, 2001 Hildinger et al. 7,196,239 B2 3/2007 Van Egmond et al.
6,248,796 B1 6, 2001 Jackson et al. 7,214,721 B2 5/2007 Eastland
6,281,158 B1 8, 2001 Gabrielov et al.
6,383,974 B1 5, 2002 Ishida et al. 7,279,019 B2 10/2007 Weedon
6,387.842 B1 5, 2002 Wegman et al. 7,638,070 B2 * 12/2009 Johnson et al. ............... 252/373
2006, OOO9537 A1 1/2006 Iordache-Cazana et al.
6,387.963 B1 5, 2002 Fitzpatrick 2007,0004809 A1 1/2007 Lattner et al.
6,444,712 B1 9, 2002 Janda 2007/0205092 A1 9/2007 Klepper
6.451,729 B1 9, 2002 Song et al.
6,616,909 B1 9, 2003 Tonkovich et al. FOREIGN PATENT DOCUMENTS
6,641,625 B1 11, 2003 Clawson et al.
6,706,770 B2 3, 2004 Patel et al. EP 1923380 5, 2008
6,753,352 B2 6, 2004 Seiki et al. JP 2004-115365. A 4/2004
6,753,353 B2 6, 2004 Jackson et al. JP 2004-339007 A 12, 2004
6,767,375 B1 T/2004 Pearson
6,818, 198 B2 11, 2004 Singh et al. OTHER PUBLICATIONS
6,858,048 B1 2, 2005 Jimeson et al.
6,863,878 B2 3, 2005 Klepper ........................ 423,650 S. Phillips et al., “Thermochemical Ethanol via Indirect Gasification
6,875,794 B2 4, 2005 Seiki et al. and Mixed Alcohol Synthesis of Lignocellulosic Biomass'. NREL
6,894,080 B2 5/2005 Seiki et al.
6,911,058 B2 6, 2005 Calderon et al. ............ 48.197 R Technical Report/TP-510.41 168 (Apr. 2007).
6,919,488 B2 7/2005 Melnichuk et al. P.L. Spath et al., Technical Report, “Preliminary Screening Tech
6,949,683 B2 9, 2005 Wieland et al. nical and Economic Assessment of Synthesis Gas to Fuels and
6,981,994 B2 1, 2006 Drnevich et al. Chemicals with Emphasis on the Potential for Biomass-Derived
6,991,769 B2 1, 2006 Kaneko et al. Syngas”, NREL Report No. NREL/TP-510-34929, Dec. 2003.
7,008,967 B2 3, 2006 Keyser et al.
7,048,772 B1 5, 2006 Bedetti * cited by examiner
U.S. Patent Apr. 10, 2012 Sheet 1 of 9 US 8,153,027 B2
U.S. Patent Apr. 10, 2012 Sheet 2 of 9 US 8,153,027 B2
U.S. Patent Apr. 10, 2012 Sheet 3 of 9 US 8,153,027 B2

22O

§ŠS, ?
220

22O
U.S. Patent Apr. 10, 2012 Sheet 4 of 9 US 8,153,027 B2

~l =No.
U.S. Patent Apr. 10, 2012 Sheet 6 of 9 US 8,153,027 B2

OL|?OuênO Jos eud O

–()–

C—OEHTY)I.,
U.S. Patent Apr. 10, 2012 Sheet 7 of 9 US 8,153,027 B2

610
N
N co
9. 6O1 -- 190
150
62O y 640
610

FIG 11
U.S. Patent Apr. 10, 2012 Sheet 8 of 9 US 8,153,027 B2

Reactor 105

1 10 / 120 125
Regg 140 Reactor Reaction
Zone

135
- -- - - m - A.----

205 810
Reaction Reaction
Zone Zone

135
- - - - A----
Reactor 105

FIG. 9
1 10 120 125
Reaction Reactor Reaction
Zone Zone
U.S. Patent Apr. 10, 2012 Sheet 9 Of 9 US 8,153,027 B2

s
5.
( )
S

S. s

D4 - |
( ) 3.
S.

S S

S
 US 8,153,027 B2
1. 2
METHODS FOR PRODUCING SYNGAS carbon monoxide and hydrogen. In some embodiments, the
added steam is present in an amount that is less than about
PRIORITY DATA 10% of such stoichiometric amount of water.
Some methods utilize carbon-containing feedstocks that
This patent application claims priority under 35 U.S.C. 5 initially contain some moisture. In some embodiments, a first
S120 from U.S. Provisional Patent Application No. 60/948, amount of steam is present from initial moisture in the car
653 for “Methods and Apparatus for Producing Syngas” bon-containing feed material, a second amount of steam is
which is hereby incorporated by reference herein for all pur added during step (a), and the combined first amount and
poses. second amount of steam is less than the Stoichiometric
10
FIELD OF THE INVENTION
amount of water to completely convert the feed material to
carbon monoxide and hydrogen. In other embodiments, the
The present invention generally relates to processes for the combined first amount and second amount of steam is greater
conversion of carbonaceous feedstocks, such as cellulosic
than the stoichiometric amount of water to completely con
biomass, into synthesis gas, and to processes for the conver 15 Vert the feed material to carbon monoxide and hydrogen.
sion of synthesis gas to products such as alcohols (e.g., etha In another aspect, the invention provides a method of form
nol). ing syngas, the method comprising the steps of
(a) devolatilizing a carbon-containing feed material to
BACKGROUND OF THE INVENTION form a gas phase and a solid phase in a devolatilization unit;
and
Synthesis gas, which is also known as syngas, is a mixture (b) passing the gas phase and the Solid phase through a
of gases comprising carbon monoxide (CO) and hydrogen heated reaction vessel to form syngas,
(H). Generally, syngas may be produced from any carbon wherein step (b) is performed in the presence of free oxy
aceous material. In particular, biomass such as agricultural gen in an amount between about 0.1% and about 50% of the
wastes, forest products, grasses, and other cellulosic material 25 Stoichiometric amount of oxygen to completely combust the
may be converted to syngas. carbon contained in the Solid phase produced in Step (a).
Syngas is a platform intermediate in the chemical and In some embodiments of this aspect, the amount of free
biorefining industries and has a vast number of uses. Syngas oxygen is less than about 25% (for example, 10-20%) of the
can be converted into alkanes, olefins, oxygenates, and alco Stoichiometric amount of oxygen to completely combust the
hols such as ethanol. These chemicals can be blended into, or 30 carbon contained in the solid phase produced in step (a). In
used directly as, diesel fuel, gasoline, and other liquid fuels. certain embodiments, the amount of free oxygen is less than
Syngas can also be directly combusted to produce heat and about 10% of the stoichiometric amount of oxygen to com
power. The substitution of alcohols in place of petroleum pletely combust the carbon contained in the Solid phase pro
based fuels and fuel additives can be particularly environmen duced in step (a).
tally friendly when the alcohols are produced from feed mate 35 Step (b) is preferably (although not necessarily) performed
rials other than fossil fuels. in the presence of Steam. In some embodiments, an initial
Improved methods are needed to more cost-effectively ratio of free oxygen to steam (O/H2O) in step (b) is less than
produce Syngas. Methods are also desired for producing Syn about 1. In some embodiments, this initial ratio is less than
gas at a greater purity and with desirable ratios of H2 to CO to about 0.5, such as between about 0.01 and about 0.2.
facilitate the conversion of syngas to other products, such as 40 Of course, it is possible to add oxygen to both steps (a) and
ethanol. (b). In some embodiments, step (a) is performed in the pres
ence of a first amount of free oxygen that is between about
SUMMARY OF THE INVENTION 0.1% and about 10% of the stoichiometric amount of oxygen
to completely combust the feed material, and step (b) is per
In one aspect, the present invention provides a method of 45 formed in the presence of a second amount of free oxygen that
forming syngas, the method comprising the steps of: is between about 0.1% and about 25% of the stoichiometric
(a) devolatilizing a carbon-containing feed material to amount of oxygen to completely combust the carbon con
form a gas phase and a solid phase in a devolatilization unit; tained in the Solid phase produced in step (a). In certain
and embodiments, the first amount of free oxygen is less than
(b) passing the gas phase and the Solid phase through a 50 about 1% of the Stoichiometric amount of oxygen to com
heated reaction vessel to form syngas, pletely combust the feed material, and the second amount of
wherein step (a) is performed in the presence of free oxy free oxygen is less than about 10% of the stoichiometric
gen in an amount between about 0.1% and about 25% of the amount of oxygen to completely combust the carbon con
Stoichiometric amount of oxygen to completely combust the tained in the Solid phase produced in step (a). When oxygen is
feed material. 55 added to both steps (a) and (b), Steam can optionally be added
In some embodiments, the amount of free oxygen is less during step (a).
than about 10% of the stoichiometric amount of oxygen to Any of the methods described above can further include the
completely combust the feed material. In other embodiments, Substeps of (i) measuring the composition of the gas phase
the amount of free oxygen is less than 0.5% of the stoichio and/or the Solid phase, (ii) determining a suitable amount of
metric amount of oxygen to completely combust the feed 60 free oxygen based on predicted partial oxidation of at least
material. In certain embodiments, the amount of free oxygen Some of the composition to syngas, and (iii) introducing a gas
is between about 2% and about 8% of the stoichiometric containing the Suitable amount of free oxygen.
amount of oxygen to completely combust the feed material. In some embodiments, devolatilizing in Step (a) can be
In some embodiments, step (a) is further performed in the performed in the presence of a catalyst. The catalyst can be
presence of added steam. The added steam can be present in 65 selected from the group consisting of potassium, potassium
an amount that is less than about 50% of the stoichiometric hydroxide, potassium carbonate, and any combinations
amount of water to completely convert the feed material to thereof.
 US 8,153,027 B2
3 4
In some embodiments, formation of syngas in step (b) can Another aspect of the invention recognizes that syngas can
be performed in the presence of a catalyst. This catalyst can be be produced during devolatilization. In some embodiments, a
selected from the group consisting of nickel, cobalt, rhodium, method is provided comprising devolatilizing a carbon-con
and all combinations and oxides thereof. taining feed material to form a gas phase and Solid phase,
The residence times of the gas phase and the Solid phase in 5 wherein the gas phase comprises syngas, and wherein the
step (a) can be substantially the same or different. In some devolatilizing is performed in the presence of free oxygen in
embodiments, the gas phase is removed, at least in part, an amount between about 0.1% and about 25% of the sto
during step (a). For example, the devolatilization unit can be ichiometric amount of oxygen to completely combust the
a multiple-stage unit in which both the gas phase and the Solid feed material. The amount of free oxygen can be about 1-10%
phase pass through at least one stage of the devolatilization 10 of the Stoichiometric amount of oxygen to completely com
unit and at least a portion of the gas phase is removed from the bust the feed material. Steam can also be added during this
devolatilization unit prior to a final stage. variation. The added steam can be present in an amount that is
In certain embodiments, free oxygen is added to the first less than about 50% of the stoichiometric amount of water to
stage only. In other embodiments, different amounts of oxy completely convert the feed material to carbon monoxide and
gen are added across multiple stages of the devolatilization 15 hydrogen.
unit. Oxygen can be added to the devolatilization unit prior to
removal of at least a portion of the gas phase. Also, after at BRIEF DESCRIPTION OF THE FIGURES
least a portion of the gas phase is removed, oxygen can be
added to the devolatilization unit. In some embodiments, a FIG. 1 shows a process flow for the production of syngas
first amount of oxygen is added prior to removal of at least a from any carbon-containing feed material, according to one
portion of the gas phase, and a second amount of oxygen is variation.
added after removal of at least a portion of the gas phase. The FIG. 2A shows a process flow for a two-stage devolatiliza
first amount of oxygen can be different than the second tion unit, according to one variation.
amount of oxygen. FIG.2B shows a side view of the two-stage devolatilization
In some embodiments, prior to step (b), the Solid phase is 25 unit shown in FIG. 2A, according to one variation.
combined with gas removed during step (a). Optionally, one FIG.3 shows a process flow for a three-stage devolatiliza
or more Substantially inert gases can be introduced after tion unit, according to one variation.
removal of at least a portion of the gas phase. FIG. 4 shows a process flow for a reformer reactor, accord
In some preferred embodiments, the presence of free oxy ing to one variation.
gen during step (a) and/or step (b) decreases the ratio of 30 FIG.5 shows a process flow for the injection of oxygen and
hydrogen to carbon monoxide in the syngas, compared to the steam into syngas that is recycled back to the devolatilization
ratio of hydrogen to carbon monoxide produced by the same unit, according to one variation.
method in the absence of oxygen. The H/CO ratio (produced FIG. 6 shows an eductor, according to one variation.
by step (b)) can be between about 0.75 and about 1.5, such as FIG. 7 shows a process flow for producing methanol and
about 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, or 1.4. In other embodiments, 35 ethanol from Syngas using two reactors in sequence, accord
the H/CO ratio produced by step (b) is higher than 1.5, but ing to one variation.
lower than the ratio that would have been produced in the FIG. 8 shows a process flow for producing methanol and
absence of free oxygen added. ethanol from Syngas using two reaction Zones in sequence in
In some preferred embodiments, the presence of free oxy a single reactor, according to one variation.
gen increases the amount of syngas produced compared to the 40 FIG. 9 shows a process flow for producing methanol and
amount of syngas produced by the same method in the ethanol from Syngas using two reactors in sequence, with at
absence of free oxygen. In some embodiments, the presence least some of the methanol produced in the first reactor
of free oxygen decreases the amount of pyrolysis products diverted from the second reactor, according to one variation.
compared to the corresponding amount produced by the same FIG. 10 shows a process flow for producing methanol and
method in the absence of free oxygen. The presence of free 45 ethanol from Syngas using two reactors in sequence accord
oxygen in step (a) and/or step (b) can also increase the syngas ing to another variation.
purity as produced in step (b). FIG. 11 shows a process flow for producing methanol and
In some embodiments, the process temperature in the ethanol from Syngas using two reactors in sequence, with the
devolatilization unit is greater than about 900°F. at least at first reactor producing methanol in high yield for conversion
one point during step (a). The maximum process temperature 50 to ethanol in the second reactor, according to one variation.
in the devolatilization unit is preferably less than about 1400° These and other embodiments, features, and advantages of
F. the present invention will become more apparent to those
In some embodiments, the process temperature in the skilled in the art when taken with reference to the following
heated reaction vessel is greater than about 1400°F. at least at detailed description of the invention in conjunction with the
one point during step (b). The maximum process temperature 55 accompanying drawings.
in the heated reaction vessel is preferably less than about
22009 F. DETAILED DESCRIPTION OF EMBODIMENTS
Some embodiments include introducing a stream produced OF THE INVENTION
in step (a) to a reactor configured with an input for a gas
comprising oxygen (such as air), wherein at least Some of the 60 Certain embodiments of the present invention will now be
stream is partially oxidized to produce additional syngas. further described in more detail, in a manner that enables the
Some other embodiments include introducing at least some of claimed invention so that a person of ordinary skill in this art
a stream produced in step (b) to a reactor configured with an can make and use the present invention.
input for a gas comprising oxygen, wherein at least some of Unless otherwise indicated, all numbers expressing reac
the stream is partially oxidized to produce additional syngas. 65 tion conditions, Stoichiometries, concentrations of compo
Of course, streams from both steps (a) and (b) could be nents, and so forth used in the specification and claims are to
partially oxidized to make syngas. be understood as being modified in all instances by the term
 US 8,153,027 B2
5 6
"about.” Accordingly, unless indicated to the contrary, the By “added steam' as used herein, it is meant steam (i.e.
numerical parameters set forth in the following specification H2O in a vapor phase) that is introduced into a system or
and attached claims are approximations that may vary apparatus in one or more input streams. Added Steam does not
depending at least upon the specific analytical technique. Any include (i) steam generated by moisture contained in the Solid
numerical value inherently contains certain errors necessarily biomass or in another material present, (ii) Steam generated
resulting from the standard deviation found in its respective by vaporization of water that may have initially been present
testing measurements. in the system or apparatus, or (iii) Steam generated by any
All publications, patents, and patent applications cited in chemical reactions that produce water.
this specification are incorporated herein by reference in their Steam reforming, partial oxidation, water-gas shift (WGS),
entirety as if each publication, patent, or patent application 10 and/or combustion reactions can occur when oxygen or steam
was specifically and individually put forth herein. are added. Exemplary reactions are shown below with respect
The following detailed description should be read with to a cellulose repeat unit (CHOs) found, for example, in
reference to the drawings, in which identical reference num cellulosic feedstocks. Similar reactions can occur with any
bers refer to like elements throughout the different figures. carbon-containing feedstock.
The drawings, which are not necessarily to scale, depict 15
Steam Reforming CHOs:-HO->6CO+6H2
selected embodiments and are not intended to limit the scope
of the invention. The detailed description illustrates by way of
example, not by way of limitation, the principles of the inven Partial Oxidation CHOs:-/3O->6CO+5H2
tion.
As used in this specification and the appended claims, the Water-Gas Shift CO+HO H+CO,
singular forms “a” “an.” and “the include plural referents Complete Combustion CHOs:-6O2->6CO+5H2O
unless the context clearly indicates otherwise. Unless defined
otherwise, all technical and scientific terms used herein have FIG. 1 illustrates an exemplary process for synthesizing
the same meaning as is commonly understood by one of syngas from biomass or another carbon-containing material.
ordinary skill in the art to which this invention belongs. If a 25 The feed material is introduced into a devolatilization unit
definition set forth in this section is contrary to or otherwise 201 through a feed section 101. The product that exits the
inconsistent with a definition set forth in patents, published devolatilization unit 201 comprises a gas phase and a solid
patent applications, and other publications that are herein phase and can further include one or more liquid phases. A
incorporated by reference, the definition set forth in this stream exiting the devolatilization unit 201 is introduced into
specification prevails over the definition that is incorporated 30 a heated reaction vessel 301, which in FIG. 1 is shown as a
herein by reference. reformer reactor, where additional syngas is produced. The
The present invention provides methods and apparatus for syngas produced in the reformer reactor 301 is introduced
producing syngas from any carbon-containing feed material. into a quench and compressing section 401, where the syngas
The present invention is premised, at least in part, on the is cooled and compressed.
addition of a Substoichiometric amount of oxygen during the 35 The “heated reaction vessel 301 is any reactor capable of
conversion of a carbon-containing feed material to syngas. causing at least one chemical reaction that produces syngas.
In some embodiments, oxygen is mixed with Steam, and Conventional steam reformers, well-known in the art, can be
the resulting mixture is added to the system for generating used either with or without a catalyst. Other possibilities
syngas. In contrast to Some prior methods that conducted the include autothermal reformers, partial-oxidation reactors,
devolatilization and reforming process for the production of 40 and multistaged reactors that combine several reaction
syngas within a controlled reducing environment, the present mechanisms (e.g., partial oxidation followed by water-gas
invention employs the concept that oxygen or oxygen-en shift). The reactor 301 configuration can be a fixed bed, a
riched air can be added to the system (i) to Supply an enthalpy fluidized bed, a plurality of microchannels, or some other
Source that displaces additional fuel requirements, e.g. by configuration. As will be further described below, heat can be
causing an exothermic reaction Such as the partial or total 45 Supplied to reactor 301 in many ways including, for example,
oxidation of carbon or devolatilization products with oxygen; by oxidation reactions resulting from oxygen added to the
(ii) to achieve a more favorable H/CO ratio in the syngas, process.
which can increase the yield of products formed from the In some variations, the syngas from the devolatilization
syngas; (iii) to increase the yield of syngas, e.g. by reducing unit 201 and/or the heated reaction vessel 301 is filtered,
the formation of less-reactive compounds and/or by convert 50 purified, or otherwise conditioned prior to being converted to
ing certain species to syngas; and/or (iv) to increase the purity another product. For example, the cooled and compressed
of syngas, e.g. by reducing the amount of CO., pyrolysis syngas may be introduced to a syngas conditioning section
products, tar, aromatic compounds, and/or other undesirable 501, where benzene, toluene, ethylbenzene, xylene, sulfur
products. compounds, nitrogen, metals, and/or other impurities or
All references herein to a “ratio of chemical species are 55 potential catalyst poisons are optionally removed from the
references to molar ratios unless otherwise indicated. For syngas. If desired, burners 601 can be used to heat the cata
example, a H2/CO ratio of 1 means one mole of hydrogen per lyst, oxygen, and/or steam that are added.
mole of carbon dioxide; an O/HO ratio of 0.1 means one Oxygen can assist pyrolysis and/or cracking reactions in
mole of molecular oxygen per ten moles of water. the devolatilization unit 201 and/or generate heat (which can
By "free oxygen, as used herein, it is meant oxygen that is 60 provide a temperature rise) from partial oxidation. As illus
contained solely in the gas phase. Free oxygen does not trated in FIG. 1, oxygen or a mixture of oxygen and steam can
include the oxygen content of the biomass itself or of any be added at any stage of the process for producing syngas. For
other solid or liquid phase present, and does not include example, oxygen may be added directly to the feed material,
oxygen that is physically adsorbed onto a Surface. Generally, to the feed section 101, before or while the feed material
'gas phase' refers to the vapor phase under the particular 65 enters the devolatilization unit 201, directly into the devola
process conditions, and will include components that are tilization unit 201, before the exhaust gas/solids from the
condensable at other conditions (such as lower temperature). devolatilization unit 201 enter the reformer reactor 301,
 US 8,153,027 B2
7 8
directly into the reformer reactor 301 (such as into the cold shown) is added between the devolatilization unit 201 and the
chambers 302 and/or hot chambers 304 of the reformer reac reformer reactor 301 or added downstream of the reformer
tor 301 shown in FIG. 4), before the syngas product from the reactor 301 (such as between the reformer reactor 301 and the
reformer reactor 301 enter the quench and compressing sec quench and compressing section 401).
tion 401, before the syngas enters the conditioning section 5 Another variation of the invention is premised on the real
501, directly into the syngas conditioning section 501, and/or ization that during devolatilization, such as in the devolatil
to one or more various recycle streams. In some embodi ization unit 201 (or another suitable devolatilization reactor
ments, oxygen or a mixture of oxygen and steam are added at or vessel), the gas phase so generated contains at least some
multiple locations. syngas. The amount and quality of syngas produced during
In some embodiments, a Substoichiometric amount of oxy 10 this step may be adjusted by oxygen and/or steam addition, in
gen is added. A "stoichiometric amount of oxygen is calcu amounts as described herein, as well as by temperature, pres
lated based on the amount of oxygen that would be required to Sure, and other conditions. The syngas from devolatilization
completely combust the feed material (entering feed section can be of Sufficient quality for Some applications. Therefore,
101) into CO, and HO; this calculation is independent of the in Some embodiments, a gas phase and Solid phase from
amount of steam that is added or the location(s) of oxygen 15 devolatilization need not proceed to a separate heated reac
addition. In some embodiments, the total amount of the oxy tion vessel (such as a steam reformer). Instead, the gas and
gen added (e.g., the Sum of the amounts of oxygen added at Solid phases may be collected and used directly; or, one or
one or more locations in the system) or the amount of oxygen both of these phases may be stored for future use.
present at any point during the process is between about 0.1% In some embodiments of the invention, the total amount of
and about 75% of the stoichiometric amount of oxygen for steam added (e.g., the sum of the amounts of steam added at
combustion. In embodiments, the amount of oxygen is less one or more locations in the system) or the amount of steam
than about any of 75%, 50%, 25%, 10%, 5%, 2%, 1%, 0.5%, present at any point during the process is at least about 0.1
or 0.1% of the stoichiometric amount of oxygen. mole of steam per mole of carbon in the feed material. In
In certain embodiments, the amount of oxygen is between various embodiments, at least about any of 0.5, 1.0, 1.5, 2.0,
about 1-25%, preferably between about 2-20%, and more 25 3.0, 4.0, 5.0, or more moles of steam are added or are present
preferably between about 5-10% of the oxygen required to per mole of carbon. In some embodiments, between about
completely combust the feed material. In other embodiments, 1.5-3.0 moles of steam are added or are present per mole
the amount of oxygen is between about 0.1-10%, preferably carbon.
between about 0.1-1%, and more preferably between about The amount to steam that is added to the heated reaction
0.1-0.5% of the oxygen required to completely combust the 30 vessel 301 can vary depending on factors such as the perfor
feed material. mance in the devolatilization unit 201. When devolatilization
In some embodiments, the amount of oxygen added spe produces a carbon-rich solid material, generally more steam
cifically to the devolatilization unit 201 is less than about any (and/or more oxygen) is used to add the necessary H and O
of 1%, 0.5%, or 0.1% of the stoichiometric amount of oxygen. atoms to the C available to generate CO and H. From the
In some embodiments, the amount of oxygen added to the 35 perspective of the overall system, the moisture contained in
reformer reactor 301 is less than about any of 25%, 10%, 5%, the feed material can be accounted for in determining how
2%, 1%, 0.5%, or 0.1% of the stoichiometric amount of much additional water (steam) to add in the process.
oxygen. In embodiments wherein oxygen is added to the Steam is generally used to steam reform, inside the
reformer reactor 301 to generate heat from exothermic partial reformer reactor 301, gases and/or solids exiting the devola
oxidation, the amount of oxygen added to the reformer reac 40 tilization unit 201. In some embodiments, steam is used, in
tor 301 can be about 1% to about 10% (such as about 5%) of part, to push feed material through the devolatilization unit
the Stoichiometric amount of oxygen. In embodiments 201. In certain embodiments, more steam is added to the
wherein oxygen is added to the reformer reactor 301 to gen reformer reactor 301 than to the devolatilization unit 201.
erate a lower ratio of H/CO in the syngas than would be In some embodiments, the humidity of the gas produced
generated in the absence of oxygen, the amount of oxygen 45 from the feed material is measured at any point in the process
added to the reformer reactor 301 can be about 10% to about and an appropriate amount of steam is added to maintain a
50% (such as about 25%) of the stoichiometric amount of desired humidity level. For example, gas from the devolatil
OXygen. ization unit 201 can be analyzed to determine the amount of
It will be appreciated by a skilled artisan that in carrying steam present and then more steam can be added, if desired.
out these methods, the amount of oxygen to be added to the 50 Exemplary ratios of oxygen added to steam added (O/
process can be calculated or estimated in a number of ways HO) are equal to or less than about any of 2, 1.5, 1, 0.5,0.2,
other than by determining overall feedstock composition. For 0.1, 0.05, 0.02, 0.01, or less. Exemplary ratios of oxygen
example, one can measure the carbon content of a feed mate added to steam present, which includes HO from moisture
rial and base the amount of oxygen on some fraction of that that was present prior to the addition of steam, any HO
which would be predicted to completely convert the carbon to 55 generated by chemical reactions, and H2O from the addition
CO. Similarly, a feedstockheating value can be determined of steam, are equal to or less than about any of 1,0.5,0.4,0.3,
and an amount of oxygen to be added can be determined. 0.2,0.1, 0.05, 0.04, 0.03, 0.02, 0.01, or less. Exemplary ratios
Alternatively, or additionally, one can measure the composi of oxygen added to steam added or present are between about
tion, carbon content, or heating value of an intermediate 0.01-2, between about 0.02-0.5, or between about 0.05-0.2.
stream or streams into which oxygen can be added. The 60 When the ratio of O/HO is greater than 1, the combustion
Substoichiometric amounts of oxygen recited herein use a reaction starts to dominate over partial oxidation, which may
basis of complete combustion for convenience only and do produce undesirably low CO/CO ratios.
not limit the scope of the invention in any way. In some embodiments, oxygen without steam is added at
Oxygen and/or steam can be present for a portion of or for one or more locations in the system. In some embodiments,
the entire time the feed material passes through the devola 65 steam without oxygen is added at one or more locations in the
tilization unit 201 and/or reformer reactor 301. In some system. In various embodiments, oxygen without steam is
embodiments, a separate partial-oxidation reactor (not added at one or more locations in the system, and steam
 US 8,153,027 B2
9 10
without oxygen is added at one or more different locations. A be faster for H/CO=1-1.5 compared to H/CO=1.5-2, for
mixture of oxygen and steam can be added at one or more certain catalysts and conditions.
locations in the system. In certain embodiments, oxygen Some embodiments of the invention provide methods of
without steam is added at one location, Steam without oxygen controlling the H2/CO ratio of the Syngas by adjusting the
is added at another location, and a mixture of oxygen and 5 amount and/or location of oxygen addition dynamically dur
steam is added at yet another location. In some embodiments, ing the process. It can be advantageous to monitor the H2/CO
a mixture of oxygen and steam is added at different O/HO ratio of the syngas in Substantially real-time, and adjust the
ratios in two or more locations.
In particular embodiments, steam is added to the devola amount and/or location of O. addition to keep the H/COratio
tilization unit 201, while oxygen is not added to the devola 10
at (or near) a prescribed level. Also, it can be beneficial to
tilization unit 201. In particular embodiments, both oxygen change the H/CO ratio in response to Some variation in the
and steam are added to the reformer reactor 301. In some process (e.g., feedstock composition changes) or variation in
embodiments, oxygen but not steam is fed to a partial-oxida conditions (e.g., catalyst deactivation), for better overall per
tion reactor that is in communication with the devolatilization formance.
unit 201 and/or reformer reactor 301. 15 Catalysts that facilitate the devolatilization, reforming,
Oxygen and steam can be added to the system as one and/or partial-oxidation reactions can optionally be provided
stream, or steam and oxygen can be injected as separate at any stage of the process for producing syngas. Referring
streams into the same or different locations. In some embodi again to FIG. 1, one or more catalysts may be added directly
ments, steam and oxygen are added in a manner that creates a to the feed material, to the feed section 101, before or while
reasonably uniform reaction Zone to avoid localized Zones of the feed material enters the devolatilization unit 201, directly
different stoichiometries in a reactor or other vessel. In some into the devolatilization unit 201, before the exhaust gas/
embodiments, oxygen and steam are added in different loca solids from the devolatilization unit 210 enter the reformer
tions such that partial oxidation and steam reforming initially reactor 301, directly into the reformer reactor 301 (e.g., addi
occur in different locations, with the resulting components tion of reforming and/or partial-oxidation catalysts can be
being later combined Such that a combination of partial oxi 25 added to the cold 302 and/or hotchambers 304 of thereformer
dation and steam reforming can occur effectively in a single reactor shown in FIG. 4) before the syngas product from the
location. reformer reactor 301 enters the quench and compressing sec
Oxygen can be added in Substantially pure form, or it can tion 401, before the syngas enters the conditioning section
be fed to the process through the addition of air, optionally 501, directly into the syngas conditioning section 501, and/or
enriched with oxygen. In some embodiments, air that is not 30 added to recycle streams. In some embodiments, one or more
enriched for oxygen is added. In other embodiments, catalysts are added at multiple locations. In some embodi
enriched air from an off-spec or recycle stream, which may be ments, a catalyst is added at the same location where oxygen
a stream from a nearby air-separation plant, for example, can or a mixture of oxygen and steam are added.
be used. In some embodiments, the use of enriched air with a Catalysts used for devolatilization include, but are not lim
reduced amount of N (i.e., less than 79 vol%) results in less 35 ited to, alkali metal salts, alkaline earth metal oxides and salts,
N in the resulting syngas. Because removal of N can be mineral Substances or ash in coal, transition metals and their
expensive, methods of producing syngas with less or no N. oxides and salts, and eutectic salt mixtures. Specific examples
are typically desirable, when the Syngas is intended for Syn of catalysts include, but are not limited to, potassium hydrox
thesis of liquid fuels such as alcohols. ide, potassium carbonate, lithium hydroxide, lithium carbon
In some embodiments, the presence of oxygen alters the 40 ate, cesium hydroxide, nickel oxide, nickel-Substituted Syn
ratio of H2/CO in the Syngas, compared to the ratio produced thetic mica montmorillonite (NiSMM), NiSMM-supported
by the same method in the absence of oxygen. The H/CO molybdenum, iron hydroxyoxide, iron nitrate, iron-calcium
ratio of the syngas can be between about 0.5 to about 2.0, such impregnated salts, nickel uranyl oxide, Sodium fluoride, and
as between about 0.75-1.25, about 1-1.5, or about 1.5-2.0. As cryolite. Devolatilization catalysis includes catalysis of
will be recognized, increased water-gas shift (by higher rates 45 devolatilization orgasification per se, as well as catalysis of
of steam addition) will tend to produce higher H/CO ratios, tar cracking reactions or pyrolysis. In some embodiments, the
such as at least 2.0, 3.0.4.0. 5.0, or even higher, which may be devolatilization catalyst is between about 1 to about 100 um
desired for certain applications. When low H2/CO ratios are in size, such as about 10-50 um. Other sizes of catalyst par
desired in the Syngas stream, it can be advantageous to ticles are, however, possible.
decrease steam addition and increase oxygen addition, as 50 Reforming and/or partial-oxidation catalysts include, but
described in various embodiments herein. are not limited to, nickel, nickel oxide, rhodium, ruthenium,
The H/CO ratio in the syngas can affect the yield of iridium, palladium, and platinum. Such catalysts can be
downstream products Such as methanol or ethanol. The pre coated or deposited onto one or more Support materials, such
ferred H/CO ratio may depend on the catalyst(s) used to as, for example, gamma-alumina (optionally doped with a
produce the desired product (from Syngas) as well as on the 55 stabilizing element such as magnesium, lanthanum, or
operating conditions. Consequently, in Some variations the barium). In some embodiments, the reforming and/or partial
production and/or Subsequent conditioning of syngas is con oxidation catalyst is between about 1 to about 1000 nm in
trolled to produce Syngas having a H2/CO ratio within a range size, such as about 10-100 nm. Other catalyst sizes are, how
desired to optimize, for example, production of methanol, ever, possible.
ethanol, or both methanol and ethanol. 60 Before being added to the system, any catalyst can be
In some variations, the H/CO ratio of the syngas produced pretreated or activated using known techniques that impact
using the methods described herein can provide an increased total Surface area, active Surface area, site density, catalyst
product (e.g., C-C alcohols) yield compared to that which stability, catalyst lifetime, catalyst composition, Surface
would be provided by Syngas produced by the corresponding roughness, Surface dispersion, porosity, density, and/or ther
methods in the absence of oxygen. This effect can be caused, 65 mal diffusivity. Pretreatments of catalysts include, but are not
for example, by faster kinetic rates toward desired products at limited to, calcining, washcoat addition, particle-size reduc
reduced H2/CO ratios; e.g., the rate of ethanol formation can tion, and Surface activation by thermal or chemical means.
 US 8,153,027 B2
11 12
Catalyst addition can be performed by first dissolving or uniform product with a lower moisture content and a higher
slurrying the catalyst(s) into a solvent Such as water or any energy content compared to the initial biomass. Torrefied
hydrocarbon that can be gasified and/or reformed. Examples biomass is hydrophobic—it does not regain humidity in Stor
of hydrocarbon Solvents include acetone, ethanol, or mixtures age and therefore is relatively stable—and will generally have
of alcohols. In some embodiments, the catalyst is added by a lower moisture content and higher energy value compared
direct injection of Such a slurry into a vessel (e.g., using to the initial biomass. In some embodiments, a feed material
high-pressure pumps such as common HPLC pumps or is torrefied before it is added to devolatilization unit 201. In
Syringe pumps). In some embodiments, the catalyst is added other embodiments, torrefaction occurs, to Some extent,
to steam and the steam/catalyst mixture is added to the sys within devolatilization unit 201.
tem. In these embodiments, the added catalyst may be at or 10 FIG. 2A depicts a devolatilization unit 201 that is con
near its equilibrium solubility in the steam or may be intro nected to the lock hopper (not shown) from the feed section
duced as particles entrained in the steam and thereby intro 101. The reaction product exiting from the devolatilization
duced into the system. unit 201 is introduced to a reformer reactor 301, according to
In some embodiments, catalysts are introduced indirectly. the embodiments depicted in these drawings. When feed
For example, catalysis may occur due to impurities present in 15 material Such as wood chips is conveyed through the devola
the feed material, from recycle streams, or from materials of tilization unit 201, it can undergo torrefaction, gasification,
construction. These indirect catalysts may or may not be and/or devolatilization. These processes reduce the mass and
beneficial. Preferably, but not necessarily, these catalyst Volume of the conveyed solids, with a corresponding increase
Sources are identified and monitored in overall process con in the mass and Volume of Volatilized gas.
trol and operation. As illustrated in FIGS. 2A and 2B, which depict the front
Catalysts can optionally be recovered from certain inter and side view of devolatilization unit 201, respectively, the
mediate or byproduct streams, such as ash from the ash devolatilization unit 201 consists of two devolatilization
quench/slag-removal system 520 (FIG. 5), using methods stacks 701, positioned next to each other. Each stack 701
known in the art. includes a series of reaction chambers 210-219. Each cham
The methods and systems of the invention can accommo 25 ber is in connection with the next chamber. Each chamber
date a wide range of feedstocks of various types, sizes, and includes one auger 220. The augers and down-corner pipes
moisture contents. Any carbon-containing compound can be distribute feed material into each devolatilization chamber
used as a feed material for the production of syngas. For 210-219 and convey the feed material flow in each devolatil
example, biomass Such as agricultural wastes, forest prod ization chamber 210-219 horizontally. An exemplary down
ucts, grasses, and other cellulosic material can be used. In 30 corner pipe is the section shown in FIG. 2A connecting cham
Some embodiments, the feedstock includes one or more mate bers 210 and 211. The augers 220 are operated by motors 222.
rials selected from timber harvesting residues, softwood A cooling-water supply that is used to cool down the motor
chips, hardwood chips, tree branches, tree stumps, leaves, temperature has an inlet 270 and an outlet 272. In some
bark, sawdust, off-spec paper pulp, corn, corn stover, wheat embodiments, motors 222 can be variable frequency drives
Straw, rice Straw, Sugarcane bagasse, Switchgrass, miscant 35 that are equipped with torque sensors at each end of the auger
hus, animal manure, municipal garbage, municipal sewage, with speed control.
commercial waste, grape pumice, almond shells, pecan In some embodiments, one or more of the augers 220 are
shells, coconut shells, coffee grounds, grass pellets, hay pel twin screws, such as a pair of overlapping or intermeshing
lets, wood pellets, cardboard, paper, plastic, and cloth. A screws mounted (e.g., a pair of screws at the same elevation or
person of ordinary skill in the art will appreciate that the 40 a pair of screws at different elevations) that are used to move
feedstock options are virtually unlimited. the feed material through the devolatilization unit 201. The
Referring to FIG. 1, the feed section 101 of FIG. 1 can twin screws are preferably designed to ensure efficient move
include a feed distribution system, a charging hopper, and a ment of feed material forward, minimize the possibility of
lockhopper (not shown), for example. In some embodiments, backward flow of material, ensure a substantially uniform
multiple charging hoppers and lock hoppers are used. Feed 45 temperature distribution in the radial direction, and/or pre
material (such as wood chips) is received from the distribu vent release of materials, thereby allowing safe operation and
tion system into the charging hopper. Each charging hopper a good operating lifetime.
feeds a lock hopper that, in turn, feeds material Such as wood Other means of conveying material through the devolatil
chips to two devolatilization stacks (701 in FIG. 2B) con ization unit 201 are certainly possible and within the scope of
tained in the devolatilization unit 201. 50 the present invention. Material can generally be conveyed by
In some embodiments, the system processes about 1 to single screws, twin screws, rams, and the like. Material can be
about 5,000 dry tons per day (“DTPD) of various timber and conveyed mechanically through the devolatilization unit 201
other biomass feed materials for conversion to syngas, which by physical force (metal contact), pressure-driven flow, pneu
is Suitable for conversion into fuel-quality alcohols such as matically driven flow, centrifugal flow, gravitational flow,
ethanol. 55 fluidized flow, or Some other known means of moving Solid
In Some embodiments, the feedstock Substantially consists and gas phases.
of Southern pine that has been chipped to a characteristic In some embodiments, the temperature within the devola
length scale of about one inch. An exemplary composition of tilization unit 201 increases as the feed material progresses
southern pine, on a dry basis, is 56 wt % carbon, 5.4 wt % through the devolatilization unit 201. In some embodiments,
hydrogen, 37 wt % oxygen, 0.4 wt % nitrogen, 0.7 wt % ash, 60 the feed material enters devolatilization unit 201 at about
and trace amounts of sulfur. Moisture levels of the feed mate ambient temperature and exits the devolatilization unit 201
rial can vary widely, depending on harvest and storage con between about 450-1000° F (such as between 900-1000°F).
dition, and can range from about 10% to about 60%. In some embodiments in which devolatilization is performed
In some embodiments, the feed material is torrefied biom in the presence of oxygen, the temperature increases due to
asS Such as torrefied wood. Torrefaction consists of a slow 65 the exothermic partial oxidization of material in the devola
heating of biomass in an inert atmosphere to a maximum tilization unit 201. In various embodiments, the pressure is
temperature of about 300° C. The treatment yields a solid between about 50 to about 200 psig, such as about 100-150
 US 8,153,027 B2
13 14
psig. Feed material is conveyed inside the tubes in the cas tilization unit 201 that the gas phase 203 is not passed through
cading auger system and is heated in the enclosed auger allows the solid phase 204 to be treated for longer in the
system. A bypass gas line can recombine recycled unreacted devolatilization unit 201.
product gas from a high-pressure separator 250 and the pro As shown in FIG. 2A, the gas phase 203 of the devolatil
cess stream and run it back through the devolatilization unit ization product leaves the devolatilization unit 201 and exits
201. from one or more top stage(s). The solid phase 204 of the
Heat is supplied to the devolatilization unit 201 by a set of devolatilization product stays in the devolatilization unit 201
burners 230, which are connected to the devolatilization unit longer and exits from the bottom stage. A two-stage devola
201 through a set of air mixers 232. Heat can be supplied in tilization unit 201 is shown in FIG. 2A wherein the top stage
two different modes: start-up and normal operation. A com 10 and the bottom stage are divided by a dashed line 202. The
mon burner system can be utilized for both modes. At start-up gas/solid separation can occur, for example, in a cyclone
heating mode, natural gas 236 is combusted and the flue gas is device that separates the gas phase from the Solid phase
primarily by density difference.
used as the hot process stream for the devolatilization unit In some embodiments, the solid phase 204 and the gas
201. During normal operation, the combustion fuel is unre 15 phase 203 enter the reformer separately, and a different
acted product gas, optionally Supplemented with natural gas. amount of oxygen and/or steam is added to the Solid phase
In some embodiments, the devolatilization burners are also 204 compared to the amount added to the gas phase 203 of the
fueled with syngas produced by the reformer reactors 301. As material leaving the devolatilization unit 201. For example,
syngas is produced, more syngas and less natural gas can be the compositions of the solid phase 204 and gas phase 203
preferably used to heat the devolatilization unit 201. leaving the devolatilization unit 201 can be measured or esti
Devolatilization outlet 235 directs devolatilization flue gas mated, and the amount of oxygen and/or steam that is added
into a devolatilization combustion-air preheater 234, where to each phase can be determined based on the composition of
the devolatilization flue gas is cooled and exchanges enthalpy each phase (such as the amount of carbon in each phase). In
with devolatilization combustionair 244, which is introduced Some embodiments, less oxygen and/or steam is added to the
into the air preheater 234 through a devolatilization combus 25 gas phase 202 than the solid phase 204. In some embodi
tion air blower 246. The preheated air is split as feed intro ments, steam is added to the gas phase 203 to enrich it towards
duced to the burners 230, as well as feed introduced directly hydrogen by the water-gas shift reaction.
to the air mixers 232. The preheated air is introduced to the air In some embodiments, steam 262 is used to obtain the
mixers 232 to combine with burner flue gases from the burn desired H/CO ratio of syngas from the reformer reactor 301.
ers 230 to help maintain the devolatilization inlet air tempera 30 The oxygen 260 can partially oxidize the devolatilization
ture. product and boost the process temperature prior to feeding to
The devolatilization combustion air preheater 234 also the reformer in order to lower the reformer burner heat duty.
directs partial preheated air into a devolatilization induced In some preferred embodiments, oxygen feed 260 (or air
draft fan 248, which can communicate with a stack 240, feed) and superheated steam feed 262 are mixed in a reformer
where the preheated air is joined with reformer flue gas 238 35 feed steam/oxygen mixer 264 and then introduced into an
that exits from the reformer reactor 301. The flue gas exiting eductor 266, where the solid phase 204 of the devolatilization
from the stack 240 exits the system through an exhaust line product from the devolatilization unit 201 joins the oxygen/
280 and through Subsequent heat-exchange equipment (not steam stream. The mixture is then introduced into the
shown). reformer reactor 301.
The devolatilization unit can be a single-stage unit or can 40 In some embodiments, the gas phase 203 of the devolatil
optionally be divided into multiple stages. For present pur ization product from the devolatilization unit 201 is combined
poses, a 'stage' is a physical Zone within the unit, and does with the solid phase 204 and the mixture is then introduced to
not relate to temporal considerations. Also, the number of the eductor 266 and the burner 268. In some other embodi
stages is independent of the number of actual augers, down ments, the gas phase 203 can be introduced into the reformer
corner pipes, stacks, or other physical implementation. Speci 45 reactor 301 directly. In some embodiments, the gas phase 203
fication and delineation of stages can be done for any purpose, is combined with oxygen and/or steam before it is introduced
Such as for temperature control, measurement points, resi into the reformer reactor 301 directly. Steam flow to the
dence-time distribution, or for the presence of various input or eductor 266 can be controlled, for example, by monitoring
output streams. concentrations of CO, H, or both. Oxygen 260 to the eductor
A multiple-stage devolatilization unit can generally be 50 266 can be controlled, for example, by the temperature down
desirable for certain feed materials for which it would be stream of the eductor 266 and/or the temperature at the
beneficial to remove some or all of the devolatilized gas prior reformer reactor 301 inlet.
to the end of the devolatilization unit 201. For example, rapid In one embodiment, reformer feed steam/oxygen mixers
removal of devolatilized gas can help prevent undesirable 264 combine oxygen and steam (which steam can be Super
gas-phase chemistry, such as polymerization leading to tar 55 heated) and introduce the mixture of steam and oxygen to the
formation. When syngas is the desired product and devolatil eductor 266. The remaining solids from the devolatilization
ization produces at least some syngas, it can be desirable to unit 201 are entrained in the gaseous volatilized products to
remove syngas upon generation rather than allowing it to the entrance of reformer reactor 301. In some embodiments
possibly react with other components present. Also, it can be when oxygen is not added prior to the reformer reactor 301, a
more energy-efficient to process the gas phase 203 for a 60 burner can be used to heat the products from the devolatiliza
shorter amount of time than the solid phase 204 in the devola tion unit 201 before they enterthereformer reactor 301. When
tilization unit 201. “Multiple stages' can mean 2, 3, 4, 5, or oxygen is added prior to the reformer reactor 301, a burner
more stages of devolatilization. can be unnecessary to heat the products from the devolatil
FIG. 2A depicts a two-stage devolatilization unit 201 such ization unit 201 before they enter the reformer reactor 301,
that the gas phase 203 and solid phase 204 exit the devolatil 65 due to the heat generated by exothermic partial oxidation.
ization unit 201 at different places. The optional passage of FIG. 3 depicts a three-stage devolatilization unit. The top
the solid phase 204 through a second portion of the devola two stages and the bottom stage are divided by dashed lines
 US 8,153,027 B2
15 16
202A and 202B. The gas phases 203A and 203B of the 318 to provide heat for reactions to form syngas can be from
devolatilization product exit from the top two stages; Solid any or all of three process sources: (1) “fresh' syngas from
phase 204A of the devolatilization product stays in the upstream sources; (2) unreacted product gas from down
devolatilization unit longer and then exits from the bottom stream synthesis; and/or (3) natural gas.
stage. The gas phases 203A and 203B may be combined after The Syngas exiting from the polishing cyclones 314 may be
they exit the devolatilization unit and before they enter the introduced to a quench and compressing section 401 of FIG.
reformer reactor 301. The gas phases 203A and 203B and 1 directly. Alternatively or additionally, syngas can first enter
solid phase 204A can be introduced into the reformer reactor into an eductor 330, where the syngas is joined with the
301 as described in reference to FIG. 2A for a two-stage oxygen/steam mixture from the reformer feed steam/oxygen
devolatilization unit. 10 mixer 264 (shown in FIG. 2A). The mixture is then optionally
FIG. 4 depicts an exemplary reformer reactor 301, which introduced to a feed/oxygen reactor 332 and ultimately into
includes five major components: a cold chamber 302, a hot the quench and compressing section 401. If desired, the oxy
chamber 304, a set of burners 318, and a set of cyclones that gen/steam mixture can also be introduced directly to both or
includes a primary cyclone 312 and a polishing cyclone 314. either chambers of the reformer reactor 301. A standard flow
A dividing wall 303 separates the cold chamber 302 from the 15 valve (not shown), or some other known means, can be used
hot chamber 304. Each chamber contains two separate ser to control the amount of the oxygen added to the system.
pentine or coiled reactor tubes 310, which increase the resi In some embodiments, reforming and partial oxidation
dence time of the products from the devolatilization unit 201 occur in the same reaction vessel. In other embodiments,
compared to the corresponding residence time for a linear reforming and partial oxidation occur in different reaction
tube. In some embodiments where the devolatilization prod vessels. For example, a partial-oxidation reactor (such as a
uct enters into the reformer reactor 301 directly, each serpen fluidized, packed-bed, or microchannel reactor) can be
tine or coiled reactor tube 310 is fed by each devolatilization upstream or downstream of the reformer reactor 301. In one
stack 701. One devolatilization stack 701 can feed one embodiment, a partial-oxidation reactor is upstream of the
reformer reactor 301. In other embodiments, each serpentine reformer reactor 301 and generates heat for reforming in the
or coiled reactor tube 310 is fed by one-half of the reaction 25 reformer reactor 301.
product from the burner 268, shown in FIG. 2A. After exiting the reformer reactor 301, syngas is preferably
Each reactor tube 310 is connected to a primary cyclone quickly cooled with water (or by some other means) to avoid
312, which is further connected to a polishing cyclone 314. formation of carbon. For example, the syngas product can be
Both cyclones remove ash from the product that exits from the cooled with boiler feed water in the quench and compressing
reactor tubes 310. In certain embodiments, about 90% and 30 section 401. In one illustrative embodiment, boiler feed water
10% by weight solids, respectively, are removed by the pri of a temperature of about 200°F. is injected directly into the
mary cyclones 312 and polishing cyclones 314. The ash is syngas stream to cool the temperature of the stream from
directed to ash collectors 316. As illustrated in FIG. 1, and about 1400°F. to about 1000°F.
described in detail herein above, oxygen or a mixture of Syngas pressure is preferably increased prior to condition
oxygen and steam may be optionally added at any point in the 35 ing. In some embodiments, the syngas is compressed to about
system, such as before, during, or after the devolatilization 1000 psig, 1500 psig, 2000 psig, or higher. In some embodi
product passes through the reformer reactor 301. ments, syngas conditioning 501 comprises feeding the syngas
In some embodiments, the reactor tubes 310 in the cold to a CO removal system (shown in FIG. 1). Any methods
chamber 302 raise the temperature of the devolatilization known in the art can be employed to remove carbon dioxide,
products from about 700-1100° F. at the entrance of the 40 including membrane-based or solvent-based separation
reformer reactor 301 to a temperature of about 1200-1500°F. methods. In some embodiments, little or no CO is removed
at the end of the cold chamber 302. In preferred embodiments, from the syngas.
the temperature is kept below the softening point of the ash In Some embodiments, the Syngas produced using the
components to facilitate their later removal. The serpentine or methods described herein has less impurities compared to
coiled reactor tubes 310 in the hot chamber 304 and their 45 syngas produced in the absence of any oxygen addition. In
contents are maintained at a constant temperature, such as Some embodiments, the decreased amount of impurities
about 1400°F. or some other suitable temperature. facilitates the further purification of syngas. For example, less
In some embodiments, the temperatures of the cold cham energy or time may be required to remove CO2 from the
ber 302 and the hot chamber 304 stay above the dew point of syngas produced using the methods described herein than
the product from the devolatilization unit 201. The tempera 50 from Syngas produced in the absence of oxygen.
ture of the hot chamber 304 can be about 1500°F., 1600°F., If desired, the removed CO can be used anywhere an inert
1700°F., or higher. Using appropriate materials, the tempera gas is desirable. For example, CO can be used to convey or
ture for the reformer reactor 301 can be about 2000°F. or even entrain Solid material from one point to another point of the
higher. In various embodiments, the pressure of the reformer process. Another use of CO, is to vary the H/CO ratio by the
reactor 301 is between about 25-500 psig, such as about 55 water-gas shift reaction. Recovered CO can also be used to
50-200 psig. The pressure of the reformer reactor 301 can be react with methane in dry reforming to produce syngas, or
the same as that for the devolatilization unit 201, in some react with pure carbon (e.g., carbon deposited on reactor
embodiments. walls or catalyst surfaces) to form 2 moles of CO in the
In some embodiments, the reforming and/or partial-oxida reverse Boudouard reaction (i.e., CO+C (2CO).
tion catalyst(s) that are (i) present in the product from the 60 In some embodiments, removed CO can be recycled back
devolatilization unit 201 or are (ii) added to the reformer to the devolatilization unit 201. Generally, a variety of purge
reactor 301, are entrained catalysts. In some embodiments, a streams from any operations downstream of the devolatiliza
fixed-bed or fluidized-bed reformer reactor 301 with one or tion can be recycled back to the devolatilization unit 201.
more reforming and/or partial-oxidation catalyst(s) is used. These purge streams may contain CO, CO, H., H2O, CH,
The reformer reactor 301 can be heated by a set of burners 65 and other hydrocarbons.
318, which are fed by fuel gas 236 and a gas mixture exiting Cooled syngas can optionally be fed to a benzene, toluene,
from a reformer air mixer 320. Fuel supplied to the burners ethylbenzene, and Xylenes removal system. In some embodi
 US 8,153,027 B2
17 18
ments, the removal system comprises a plurality of activated into the eductor. An angle of greater than 90 degrees, and up
carbon beds. Of course, other organic compounds (such as to 180 degrees, represents injection of the suction fluid in a
tars) can be removed as well, depending on conditions. direction flowing upstream relative to the movement of the
FIG. 5 depicts certain embodiments for devolatilization motive phase. Exemplary angles of entry in various embodi
and reforming. The feed material is introduced into a devola 5 ments include angles between about 10 to about 60 degrees,
tilization unit 201. The product that exits from the devolatil and in certain embodiments, the angle is about any of 30, 35,
ization unit 201 is introduced into a reformer reactor 301, 40, or 45 degrees.
where syngas is produced. The syngas produced in the While FIG. 6 shows two streams 610 entering the eductor
reformer reactor 301 is introduced into a primary cyclone 312 600, other embodiments can include 1, 3, 4, 5, or more loca
and a polishing cyclone 314, where ash and other solids are 10 tions where suction-fluid enters the eductor 600. By “streams
removed from the syngas product. The Syngas that exits from 610 it is meant any number of actual streams, including a
the polishing cyclone 314 is introduced to a quench and single stream of suction fluid. These different entries can all
compressing section 401, where the syngas is cooled and be characterized by the same angle. Alternatively, different
compressed. The Solids separated from the syngas product in angles may be used.
the primary cyclone 312 are introduced into an ash-quench/ 15 According to embodiments of the present invention,
slag-removal system 520, where oxygen or a mixture of oxy stream 601 can be at least a portion of the solid-vapor mixture
gen and steam can be injected. The mixture of oxygen and exiting the devolatilization unit 201. Stream 601 can enter the
steam allows the Solids separated from the syngas to undergo eductor 600 by means of a single-screw (auger) conveyer, a
partial oxidation. The gas product from the ash-quench/slag twin-screw device, or by any other means. Streams 610 can be
removal system 520 is introduced to an eductor 900, which one or more of steam, oxygen, and air. The amount of steam
helps the gas product transfer back to the devolatilization unit or oxygen to inject by means of streams 610 can be the
201. The gas product circulating back from the ash-quench/ amount that is desired for the steam reforming and/or partial
slag removal system 520 helps to move forward the material oxidation steps downstream of the devolatilization unit 201,
in the devolatilization unit 201. In one embodiment, the gas or can be a different amount.
product from the ash-quench/slag removal system 520 enters 25 In addition to adding reactants to the process, streams 610
the devolatilization unit 201 near the exit of the devolatiliza also can enhance mixing efficiency within the eductor 600, so
tion unit. The Solids further separated in the ash-quench/slag that species can be well-mixed upon entering the reformer
removal system 520 are removed at the bottom of the system. reactor 301. Without being limited to any particular theory, it
Another aspect of the present invention relates to eductors. is believed that the solid material entering in stream 601 is
Eductors (also known as jet ejector pumps or Venturi pumps) 30 characterized by laminar flow or plug flow; the suction fluid
are an efficient way to pump or move many types of liquids from 610 is thought to cause an onset of turbulent flow within
and gases. Eductors generally utilize the kinetic energy of one the eductor 600. Turbulence is known to enhance mixing and
species to cause the flow of another. In operation, the pressure can also help break apart the solids and reduce particle size.
energy of the motive liquid is converted to Velocity energy by The exact nature of this onset of turbulence is generally a
a converging nozzle. The high Velocity flow then entrains 35 function of the velocity and pressure of streams 601 and 610,
another species (such as Solids from the devolatilization unit the areas 640 and 150, the angle 620 (or plurality of angles),
201). The mixture is then converted back to an intermediate and the nature of the motive and suction fluids. The eductor
pressure after passing through a diffuser. Eductors can also 600 can also be suitable for multiphase annular flow from the
balance pressure drops and aid in overall heat transfer. devolatilization unit 201 to said heated reaction vessel 301.
In some embodiments, the eductor is used to convey the 40 As will be appreciated, other gases besides HO and O for
material leaving the devolatilization unit 201 and entering the streams 610 can additionally or alternatively be used. Other
reformer reactor 301 (such as eductor 266 shown in FIG. 2A). gases that could be used include, but are not limited to,
In certain embodiments, the drive gas for this eductor is steam recycled syngas, recycled steam possibly containing various
and/or oxygen that is introduced into the reformer reactor impurities, such as CO, N, methanol vapor, ethanol vapor,
301. 45 etc.
An eductor 600 that can be used in particular embodiments The eductor 600 can be employed in any step of the process
is depicted in FIG. 6, which is exemplary and non-limiting. described herein, such as the removal of ash-rich solids or
With reference to FIG. 6, generally solids and (if present) other purge streams (such as eductor 330 in FIG. 4) or the
gases enter as stream 601, which can be referred to as the mixing of oxygen and steam with Syngas (Such as eductor 900
motive phase. In some embodiments, additional vapor is 50 in FIG. 5). Eductor 600 can also be used in any other appa
added in streams 610, which collectively can be referred to ratus for which an eductor is desirable, such as an apparatus
interchangeably as the suction fluid, the educted fluid, or the for which one or more decreases in pressure within the appa
eductor drive fluid. ratus is desirable.
The eductor 600 in FIG. 6 is characterized by a first cross Exemplary methods and apparatus for producing alcohols
sectional area 640 and a second, Smaller cross-sectional area 55 from Syngas are disclosed herein. In some variations of these
150. The area reduction causes a lower pressure, which cre methods and apparatus, syngas is catalytically converted to
ates a suction effect to pull material forward. The material methanol in a first reaction Zone, and residual syngas from the
velocity increases through the smaller area 150, and then first reaction Zone is then catalytically converted to ethanol in
returns to a lower velocity downstream of the area reduction, a second reaction Zone. Referring to FIG. 7, for example, in
according to a momentum balance. Stream 190 exits the 60 one variation a syngas feedstream 100 is introduced into a
eductor 600. first reactor 105 comprising a first reaction Zone 110. One or
Streams 610 are shown in FIG. 6 to enter at an angle more catalysts in reaction Zone 110 convert at least a portion
denoted 620. This angle can be any angle but in some embodi of syngas feedstream 100 to methanol to provide an interme
ments is greater than about 0 degrees and less than about 90 diate product stream 115 comprising at least a portion of the
degrees. An angle of 0 degrees produces co-incident flow of 65 residual (unreacted) syngas from feedstream 100, methanol,
the suction fluid and the motive phase, while an angle of 90 and, in Some variations, higher alcohols and/or other reaction
degrees produces perpendicular injection of the Suction fluid products.
 US 8,153,027 B2
19 20
At least a portion of intermediate product stream 115 is Basic promoters include alkaline-earth and rare-earth metals.
introduced into a second reactor 120 comprising a second Non-metallic bases can also serve as effective promoters in
reaction Zone 125. One or more catalysts in reaction Zone 125 Some embodiments.
convert at least a portion of syngas from intermediate product In some variations, up to about 50% of CO in syngas
stream 115 and/or at least a portion of methanol from inter feedstream 100 is converted to methanol in reaction Zone 110.
mediate product stream 115 to provide a product stream 130 Intermediate product stream 115 output from reactor 105 may
comprising ethanol and, in Some variations, methanol, higher comprise, in some variations, about 5% to about 50% metha
alcohols, other reaction products, and/or unreacted syngas nol, about 5% to about 50% ethanol, about 5% to about 25%
from intermediate product stream 115. CO, about 5% to about 25% H, and about 2% to about 35%
Various components of product stream 130 such as, for 10 CO, as well as other gases. In some embodiments, interme
example, methanol, ethanol, alcohol mixtures (e.g., metha diate product stream 115 also comprises one or more higher
nol, ethanol, and/or higher alcohols), water, and unreacted alcohols, such as ethanol, propanol, or butanol.
syngas may be separated out and (optionally) purified by the The H/CO ratio in intermediate product stream 115 can, in
methods described herein or conventional methods. Such
some variations, affect the yield of ethanol and other products
15 in reactor 120. The preferred H/CO ratio in such variations
methods may include, for example, condensation, distilla may depend on the catalyst or catalysts used in reactor 120 as
tion, and membrane separation processes, as well as drying or well as on the operating conditions. The H/CO ratio in inter
purifying with molecular sieves. mediate product stream 115 can differ from that offeedstream
Syngas feedstream 100 may be produced in any suitable 100 as a result of reactions occurring in reactor 105. In some
manner known to one of ordinary skill in the art from any variations, the H/CO ratio of intermediate product stream
suitable feedstock. In some variations, syngas feedstream 100 115 provides a higher ethanol yield in reactor 120 than would
is filtered, purified, or otherwise conditioned prior to being the H/CO ratio offeedstream 100. In such variations, opera
introduced into reactor 105. For example, carbon dioxide, tion of reactor 105 to produce methanol, for example,
benzene, toluene, ethylbenzene, Xylenes, Sulfur compounds, improves the H/CO ratio of the syngas fed to reactor 120
metals, and/or other impurities or potential catalyst poisons 25 from the standpoint of ethanol yield in reactor 120.
may be removed from syngas feedstream 100 by conventional In one example, feedstream 100 comprises syngas with an
methods known to one of ordinary skill in the art. H/CO ratio of about 1.5 to about 2, and the preferred H/CO
In some variations, syngas feedstream 100 comprises H. ratio for production of ethanol in reactor 120 is about 1.
and COatan H/CO ratio having a value between about 0.5 to Operation of reactor 105 to produce methanol, in this
about 3.0, about 1.0 to about 1.5, or about 1.5 to about 2.0. The 30 example, depletes H. in the syngas which decreases the
H/CO ratio in feedstream 100 can, in some variations, affect H/CO ratio in intermediate product stream 115 to a value
the yield of methanol and other products in reactor 105. The closer to 1 and thus improves the ethanol yield in reactor 120.
preferred H/CO ratio in such variations may depend on the In certain embodiments, the catalyst is a Cu/ZnO/alumina
catalyst or catalysts used in reactor 105 as well as on the catalyst.
operating conditions. Consequently, in Some variations, the 35 Reactor 120 may be any type of catalytic reactor suitable
production and/or Subsequent conditioning of syngas feed for the conversion of syngas, methanol, and/or syngas plus
stream 100 is controlled to produce syngas having a H/CO methanol to ethanol and, optionally, to higher alcohols and/or
ratio within a range desired to optimize, for example, produc other products. Reactor 120 may be any suitable fixed-bed
tion of methanol, ethanol, or both methanol and ethanol. reactor, for example. In some variations, reactor 120 com
Syngas feedstream 100 may optionally be pressurized and/ 40 prises tubes filled with one or more catalysts. Syngas and/or
or heated by compressors and heaters (not shown) prior to methanol passing through the tubes undergoes surface cata
entering reactor 105. In some variations, syngas feedstream lyzed reactions to form ethanol and, in some variations,
100 enters reactor 105 at a temperature of about 300° F. to higher alcohols and/or other products. While not intending to
about 600°F. and at a pressure of about 500 psig to about 2500 be bound by any particular theory, it is presently believed that
pS1g. 45 the methanol may be converted to syngas and thence to etha
Reactor 105 may be any type of catalytic reactor suitable nol, the methanol may be converted directly to ethanol via a
for the conversion of syngas to methanol, alcohol mixtures homologation reaction, and/or the methanol may be con
comprising methanol, higher alcohols, and/or other products. verted to ethanol by other mechanisms. Reactor 120 may
Reactor 105 may be any suitable fixed-bed reactor, for operate, for example, at temperatures of about 500 F. to
example. In some variations, reactor 105 comprises tubes 50 about 800°F. and at pressures of about 500 psig to about 2500
filled with one or more catalysts. Syngas passing through the pS1g.
tubes undergoes catalyzed reactions to form methanol and, in Any suitable catalyst or combination of catalysts may be
Some variations, higher alcohols or other products. In some used in reactor 120 to catalyze reactions converting syngas,
embodiments, catalysis occurs within pellets or in a homo methanol, and/or syngas--methanol to ethanol and, option
geneous phase. Reactor 105 may operate, for example, at 55 ally, to higher alcohols and/or other products. Suitable cata
temperatures of about 400°F. to about 700°F. and at pres lysts may include, but are not limited to, alkali/ZnO/Cr2O,
sures of about 500 psig to about 2500 psig. Cu/ZnO, Cu/ZnO/Al2O, CuO/CoO, CuO/CoO/Al2O,
Any suitable catalyst or combination of catalysts may be Co/S, Mo/S, Co/Mo/S, Ni/S, Ni/Mo/S, Ni/Co/Mo/S, Rh/Ti/
used in reactor 105 to catalyze reactions converting syngas to SiO, Rh/Mn/SiO, Rh/Ti/Fe/Ir/SiO, Rh/Mn/MCM-41, Cu,
methanol and, optionally, to higher alcohols and/or other 60 Zn, Rh, Ti, Fe, Ir, and mixtures thereof. The addition of basic
products. Suitable catalysts may include, but are not limited promoters (e.g. K. Li, Na, Rb, Cs, and Fr) may increase the
to, one or more of ZnO/Cr2O, Cu/ZnO, Cu/ZnO/Al2O, activity and selectivity of some of these catalysts for ethanol
Cu/ZnO/CrO, Cu/ThC), Co/Mo/S, Co/S, Mo/S, Ni/S, or other Calcohols. Basic promoters include alkaline-earth
Ni/Mo/S, Ni/Co/Mo/S, Rh, Ti, Fe, Ir, and any of the foregoing and rare-earth metals. Non-metallic bases can also serve as
in combination with Mn and/or V. The addition of basic 65 effective promoters, in Some embodiments.
promoters (e.g. K. Li, Na, K, Rb, Cs, and Fr) increases the In some embodiments, catalysts for reactor 120 include
activity and selectivity of some of these catalysts for alcohols. one or more of ZnO/Cr2O, Cu/ZnO, Cu/ZnO/Al2O, CuO/
 US 8,153,027 B2
21 22
CoO, CuO/CoO/Al2O, Co/S, Mo/S, Co/Mo/S, Ni/S, Ni/Mo/ alcohols, other reaction products, and/or unreacted syngas
S, Ni/Co/Mo/S, Rh/Ti/SiO, Rh/Mn/SiO, Rh/Ti/Fe/Ir/SiO, from intermediate product stream 115.
Rh/Mn/MCM-41, Ni/Mo/S, Ni/Co/Mo/S, and any of the Reactor 200 may be any type of suitable catalytic reactor
foregoing in combination with Mn and/or V. Again, any of comprising two or more reaction Zones. Operation of reactor
these catalysts can (but do not necessarily) include one or 5 200 may be similar to the operation of reactors 105 and 120
more basic promoters. described above. In particular, in some variations, the cata
Product stream 130 output from reactor 120 may comprise, lysts used in reactions Zones 205 and 810 and the operating
in some variations, about 0% to about 50% methanol, about conditions for the reaction Zones are the same as or similar to
10% to about 90% ethanol, about 0% to about 25% CO, about those for, respectively, reaction Zones 110 and 120 described
0% to about 25% Handabout 5% to about 25% CO, as well
10 above. The compositions of intermediate product stream 115
as other gases. In some embodiments, product stream 130 and product stream 130 may, in some variations, be the same
as or similar to those for the variations described above with
also comprises one or more higher alcohols, such as propanol respect to FIG. 7. Syngas in product stream 130 may be
or butanol.
recycled through reaction Zone 810 or added to feedstream
Referring again to FIG. 7, in Some variations unreacted 15 100. CO may be added to syngas feedstream 100, or the
syngas in product stream 130 is separated from product production and/or Subsequent conditioning of syngas feed
stream 130 to form feedstream 135 and recycled through stream 100 may be controlled to produce syngas having a
reactor 120 to further increase, for example, the yield of desirable amount of CO for enhanced methanol production.
ethanol and/or other desired products. Alternatively, or in A methanol feedstream (not shown) may be introduced to
addition, in Some variations unreacted syngas in product reaction Zone 810 to further increase, for example, the yield of
stream 130 is recycled through reactor 105 by adding it to ethanol and/or other desired products. This methanol feed
syngas feedstream 100. The latter approach may be unsuit stream may be, for example, separated from product stream
able, however, if the unreacted syngas in product stream 130 130.
is contaminated, for example, with Sulfur, Sulfur compounds, Similarly to the two-reactor variations, in some of the
metals, or other materials that can poison methanol catalysts 25 single-reactor variations the H/CO ratio in intermediate
in reactor 105. product stream 115 can affect the yield of ethanol and other
Also, in some variations a methanol feedstream 140 is products in reaction Zone 810. In some variations, the H/CO
added to intermediate product stream 115 or otherwise intro ratio of intermediate product stream 115 differs from that of
duced to reactor 120 to further increase, for example, the yield feedstream 100 and provides a higher ethanol yield in reac
of ethanol and/or other desired products. For example, metha 30 tion Zone 810 than would the H/CO ratio offeedstream 100.
nol in product stream 130 may be separated (not shown) from In Such variations, production of methanol in reaction Zone
product stream 130 to form feedstream 140 and then recycled 205, for example, improves the H/CO ratio of the syngas fed
through reactor 120. Methanol from other sources may be to reaction Zone 810 from the standpoint of ethanol yield in
introduced into reactor 120, as well or instead. reactor 120.
In some variations, one or more catalysts in reactor 105. 35 Referring now to FIG.9, some alternative variations differ
one or more catalysts in reactor 120, or one or more catalysts from those described with respect to FIG. 7 in that at least a
in both reactor 105 and reactor 120 catalyze the conversion of portion (some or substantially all) of the methanol in inter
CO to methanol. Production of methanol in reactor 105, mediate product stream 115 is diverted into a methanol prod
reactor 120, or in both reactors may be thereby enhanced by uct stream 300 prior to the introduction of product stream 115
consumption of CO present in syngas feedstream 100. Con 40 into reactor 120. Methanol in product stream 300 can be
sequently, in Some variations, CO is added to syngas feed separated and purified by conventional methods, for example.
stream 100, or the production and/or Subsequent conditioning As above, in some of these variations the H/CO ratio of
of syngas feedstream 100 is controlled to produce syngas intermediate product stream 115 differs from that of feed
having a desirable amount of CO. Suitable catalysts for stream 100 and provides a higher ethanol yield in reactor 120
converting CO to methanol may include, in some variations, 45 than would the H/CO ratio of feedstream 100. Hence, the
one or more of those listed above for use in reactors 105 and production of methanol in reactor 105 may advantageously
120. Enhanced production of methanol by consumption of enhance ethanol production in reactor 120 in some of these
CO may result, in Some variations, in enhanced production variations.
of ethanol by conversion of the methanol to ethanol and/or by In some variations methanol is produced at high yield in a
a resulting favorable adjustment of the H/CO ratio in the 50 first reactor and Subsequently converted to ethanol in a second
syngas stream introduced to reactor 120. reactor. Referring to FIG. 11, for example, in some variations
Referring now to FIG. 8, some alternative variations differ a syngas feedstream 100 is catalytically converted to metha
from those described above primarily by use of a single nol in a first reactor 105 at a yield (mole conversion of CO to
reactor 200 comprising a first reaction Zone 205 and a second methanol) of, for example, at least 50%, 75%, 85%, 95%, or
reaction Zone 810 rather than two reactors. Syngas feed 55 higher, Subject to equilibrium constraints. High methanol
stream 100 is introduced into first reaction Zone 205, where yields may be facilitated, for example, by separating out some
one or more catalysts convert at least a portion of syngas or Substantially all of the non-methanol components in inter
feedstream 100 to methanol to provide intermediate product mediate product stream 115 as a stream 500 that is recycled
stream 115 (comprising at least a portion of the unreacted through reactor 105.
syngas from feedstream 100, methanol and, in Some varia 60 An unrecycled portion of intermediate product stream 115,
tions, higher alcohols and/or other reaction products). At least rich in methanol, is (optionally) mixed with another syngas
a portion of intermediate product stream 115 is introduced feedstream 510 to provide feedstream 515 which is intro
into second reaction Zone 810, where one or more catalysts duced into reactor 120. At least a portion of the methanol and
convert at least a portion of syngas from intermediate product (optionally) syngas introduced into reactor 120 are catalyti
stream 115 and/or at least a portion of methanol from inter 65 cally converted to provide a product stream 130 comprising
mediate product stream 115 to form product stream 130 com ethanol and, in some variations, methanol, higher alcohol,
prising ethanol and, in Some variations, methanol, higher other reaction products, and/or unreacted syngas from feed
 US 8,153,027 B2
23 24
stream 515. In some variations, unreacted syngas in product Heated syngas 415 from preheater 410 is sent to a set of
stream 130 is recycled through reactor 120 as feedstream 135 reactor guard beds 420, 425. Guard beds 420, 425 can be
and/or recycled through reactor 105. Various components of configured in a permanent lead-lag arrangement but are piped
product stream 130 may be separated out and/or purified as Such that either bed can be bypassed. The piping arrangement
described above, for example. 5 allows one bed to be in service while the other is being
In some variations, the ratio of methanol to CO in a feed regenerated or activated. Regeneration/activation is initiated
stream may be adjusted, for example, to optimize the yield of by a mixed hydrogen and nitrogen line (not shown). Guard
ethanol in reactor 120. In some embodiments, the ratio of beds 415, 420 remove, for example, sulfurs and metals that
methanol/CO in reactor 120 is between about 0.5 to about 2.0. may poison the methanol catalysts. In some embodiments,
In particular embodiments, the ratio of methanol/CO in reac 10 one or more catalyst poisons are removed by adsorption over
tor 120 is about 1.0. copper, copper chromite, nickel, cobalt, or molybdenum.
Any suitable catalyst or combination of catalysts may be These and other metals can be supported on high-Surface-area
used in reactor 105. Suitable catalysts for reactor 105 may refractory inorganic oxide materials such as alumina, silica,
include, but are not limited to, the methanol catalysts listed silica/alumina, clays, or kieselguhr. One exemplary material
above. Similarly, any suitable catalyst or combination of cata 15 is copper on alumina.
lysts may be used in reactor 120. Suitable catalysts for reactor Exit gases 430 from guard beds 420, 425 are sent to an
120 may include, but are not limited to, the ethanol catalysts alcohol reactor cross exchanger 435 at about 350° F. and are
listed above. heated to about 480° F. during heat exchange with crude
The composition of catalysts in reactors 105 and 120, or alcohol exit gases 470 from second alcohol reactor 460.
reaction Zones 110 and 125, can be similar or even the same. Syngas at about 1500 psig and about 480° F. enters a first
Reference to a “first catalyst” and “second catalyst” in con alcohol synthesis reactor 440, where at least a portion of the
junction with reaction Zones is a reference to different physi syngas undergoes a Surface-catalyzed reaction in Supported
cal materials, not necessarily a reference to different catalyst catalyst tubular reactors within the reactor vessel. In some
compositions. variations, the catalyst in reactor 440 is a Cu/ZnO/alumina
In variations of any of the methods described herein that 25 catalyst. Methanol is expected to be formed via the reaction
use a first reaction Zone and a second reaction Zone, the initial CO+2H->CHOH. In some variations methanol may be
syngas stream is introduced into both the first reaction Zone formed, as well, by hydrogenation of CO.
and the second reaction Zone. Such as the independent intro Product gases 450 leave alcohol synthesis reactor 440 at a
duction of syngas into both the first reaction Zone and the temperature of about 500 F. and enter alcohol synthesis
second reaction Zone. In some embodiments, the syngas is 30 reactor 460. In addition, a methanol stream 465 (e.g., a metha
from an external source. In some embodiments, the Syngas is nol recycle stream separated from crude alcohol stream 470)
from any of the methods described herein (such as residual is mixed with the product gases 450 from reactor 440 and also
syngas from a first reaction Zone or a second reaction Zone). introduced to reactor 460. Reactions occurring in reactor 460
In some embodiments of any of the methods described include ethanol formation at about a 40% molar conversion
herein, Syngas from any source is added to the first reaction 35 basis of methanol entering reactor 460.
Zone and/or the second reaction Zone. In some embodiments Crude alcohol stream 470 exits reactor 460 at a temperature
of any of the methods described herein, methanol from any of about 650 F. and is cooled by heat exchange in alcohol
Source is added to the second reaction Zone. reactor cross exchanger 435 to a temperature of about 530°F.
Certain embodiments employ a plurality of physical reac Subsequent heat recovery and other cooling steps (not shown)
tors in one or both of the reaction Zones. For example, the first 40 cool crude alcohol stream 470 to about 100°F.
Zone could consist of two reactors, followed by a single Ethanol, methanol, residual syngas, and other components
reactor as the second Zone. Or, in another example, the first of crude alcohol stream 470 may be separated and (option
Zone could be one reactor followed by two reactors in the ally) purified by using the methods described herein or using
second Zone. In general, any "Zone' or “reaction Zone' can conventional methods (not shown). Syngas recovered from
contain a fraction of one, two, three, or more physical reac 45 stream 470 may be recycled through the reactors by mixing it
tOrS. with syngas feedstream 400, for example.
In some embodiments of any of the methods described In some embodiments, ethanol is purified from the product
herein, reaction conditions (such as temperature and pres stream 130 or crude alcohol stream 470 by first drying the
Sure) used for the conversion of syngas to methanol, the product stream 130 or crude alcohol stream 470 to produce an
conversion of syngas and/or methanol to ethanol, or the 50 intermediate product, and then distilling the intermediate
homologation of methanol to ethanol, are the same as those product to produce a purified ethanol product. In some
described in any of U.S. Pat. Nos. 4,371,724; 4,424,384; embodiments, the product stream 130 or crudealcohol stream
4,374,285; 4,409,405; 4,277,634; 4,253,987; 4,233,466; and 470 comprises or consists of ethanol, methanol, propanol,
4,171.461; all of which are incorporated by reference herein butanol, and water. In some embodiments, product stream
in their entirety. If desired, one skilled in the art can adjust 55 130 or crude alcohol stream 470 includes one or more of the
reaction conditions using standard methods to improve the following alcohols: 1-propanol. 2-propanol, 1-butanol, 2-bu
production of methanol and/or ethanol. tanol, t-butanol, pentanols, hexanols, heptanols, and octanols,
FIG. 10 shows another example, in more detail than above, and/or higher alcohols. In some embodiments, product
of a process in which syngas is catalytically converted to stream 130 or crude alcohol stream 470 includes one or more
methanol in a first reactor, and methanol and residual syngas 60 aldehydes, ketones, and/or organic acids (such as formalde
from the first reactor are converted to ethanol in a second hyde, acetaldehyde, acetic acid, and the like).
reactor. Referring now to FIG. 10, a single two-stage inter In particular embodiments, the drying step reduces the
cooled reciprocating compressor 405 compresses syngas amount of water in the product stream 130 or crude alcohol
feedstream 400 to about 1500 psig and feeds it at a tempera stream 470 by at least about 75%, 95%, or more. In particular
ture of about 135°F. to syngas preheater 410. Preheater 410 is 65 embodiments, the amount of the water is less than or equal to
a shell and tube heat exchanger that uses steam as an enthalpy about 5% or preferably about 0.5% of the intermediate prod
SOUC. uct by weight.
 US 8,153,027 B2
25 26
In some embodiments, the drying step involves passing the is the intent that this patent will cover those variations as well.
product stream 130 or crude alcohol stream 470 through a The present invention shall only be limited by what is
membrane, such as Zeolite membrane, or through one or more claimed.
molecular sieves to produce an intermediate product. Con What is claimed is:
ventional distillation methods can be used to distill the inter 1. A method of forming syngas, said method comprising
mediate product. In some embodiments, the distillation con the steps of:
ditions are adjusted using standard methods based on the (a) devolatilizing a carbon-containing feed material to
contents and/or purity of the distilled product being produced form a gas phase and a solid phase in a devolatilization
to increase the purity of ethanol in the final product. In some unit, wherein said devolatilization unit includes a cas
embodiments, ethanol is between about 95% to about 99.9%
10 cading series of devolatilization chambers with augers
of the purified ethanol product by weight. for conveying said carbon-containing feed material
In some embodiments of the invention, one or more param through said devolatilization chambers at increasing
temperatures; and
eters are varied to improve or optimize the generation of (b) passing said gas phase and said Solid phase through a
syngas or downstream products (such as ethanol). For 15 heated reaction vessel to form syngas, wherein said
example, one or more parameters can be adjusted during the heated reaction vessel includes a cold chamber, a hot
conversion of a feed material to syngas. In some embodi chamber separated from said cold chamber; a reaction
ments, a feed material is converted to syngas using one set of tube traversing through said cold and hot chambers; a
conditions, and then the method is repeated for the same type primary cyclone, connected to said reaction tube, for
of feed material, or another type of feed material, under a removing ash; and a polishing cyclone, connected to
different set of conditions to improve the production of syn said primary cyclone, for removing additional ash;
gas. Standard statistical methods can be used to help deter wherein step (a) is performed in the presence of free oxy
mine which parameters to vary and how to vary them. In gen in an amount between about 0.5% and about 25% of
general, economics will dictate the selection of process the stoichiometric amount of oxygen to completely
parameters. 25 combust said feed material;
In some embodiments, one or more of the following wherein the temperature of said heated reaction vessel is
parameters are varied: type of feed material, composition of controlled to be above the dew point of said gas phase
feed material, amount of oxygen, location(s) in which oxygen from said devolatilization unit; and
is added, amount of Steam, location(s) in which steam is wherein a portion of said syngas is recycled back to said
30 devolatilization unit.
added, ratio of oxygen to steam, temperature profile, pressure
profile, type of catalyst, composition of catalyst, catalyst 2. The method of claim 1, wherein said amount of free
concentration profile, location(s) in which catalyst is added, oxygen is less than about 10% of the stoichiometric amount of
catalyst activity, average residence time, and residence-time oxygen to completely combust said feed material.
3. The method of claim 2, wherein said amount of free
distribution. Initial values or ranges for any of these input 35 oxygen is less than about 1% of the stoichiometric amount of
parameters can be selected based on the values described oxygen to completely combust said feed material.
herein. 4. The method of claim 2, wherein said amount of free
In some embodiments, the variation in one or more of these oxygen is greater than about 1% of the Stoichiometric amount
parameters improves one or more of the following: yield of of oxygen to completely combust said feed material.
the syngas; rate of conversion to the syngas; ratio of H2/CO in 40 5. The method of claim 2, wherein said amount of free
the syngas at one or more points; average and/or dynamic oxygen is between about 2% and about 8% of the stoichio
concentration profiles of CO, H, O, CO, H.O. output cata metric amount of oxygen to completely combust said feed
lyst composition; overall and/or unit-specific energy balance; material.
overall and/or unit-specific mass balance; economic output; 6. The method of claim 1, wherein step (a) is further per
yield of one or more products from Syngas, such as C-C, 45 formed in the presence of added steam.
alcohols (e.g., more particularly, ethanol); product selectiv 7. The method of claim 6, wherein a first amount of steam
ity; or rate of production of one or more desired compounds. is present from initial moisture in said carbon-containing feed
In this detailed description, reference has been made to material, a second amount of steam is added during step (a),
multiple embodiments of the invention and non-limiting and the combined first amount and second amount of steam is
examples relating to how the invention can be understood and 50 less than the Stoichiometric amount of water to completely
practiced. Other embodiments that do not provide all of the convert said feed material to carbon monoxide and hydrogen.
features and advantages set forth herein may be utilized, 8. The method of claim 1, wherein said devolatilization unit
without departing from the spirit and scope of the present is a multiple-stage unit in which both said gas phase and said
invention. This invention incorporates routine experimenta Solid phase pass through at least a first stage of said devola
tion and optimization of the methods and systems described 55 tilization unit and at least a portion of said gas phase is
herein. Such modifications and variations are considered to removed from said devolatilization unit prior to a final stage
be within the scope of the invention defined by the claims. during step (a).
Where methods and steps described above indicate certain 9. The method of claim 8, wherein said free oxygen is
events occurring in certain order, those of ordinary skill in the added to said first stage only.
art will recognize that the ordering of certain steps may be 60 10. The method of claim 7, wherein prior to step (b), said
modified and that Such modifications are in accordance with Solid phase is combined with said at least a portion of said gas
the variations of the invention. Additionally, certain of the phase removed during step (a).
steps may be performed concurrently in a parallel process 11. A method of forming syngas, said method comprising
when possible, as well as performed sequentially. the steps of:
Therefore, to the extent that there are variations of the 65 (a) devolatilizing a carbon-containing feed material to
invention, which are within the spirit of the disclosure or form a gas phase and a solid phase in a devolatilization
equivalent to the inventions found in the appended claims, it unit, wherein said devolatilization unit includes a cas
 US 8,153,027 B2
27 28
cading series of devolatilization chambers with augers amount of free oxygen that is between about 0.5% and about
for conveying said carbon-containing feed material 25% of the stoichiometric amount of oxygen to completely
through said devolatilization chambers at increasing combust the carbon contained in said Solid phase produced in
temperatures; and step (a).
(b) passing said gas phase and said solid phase through a 15. The method of claim 14, wherein said first amount of
heated reaction vessel to form syngas, wherein said free oxygen is less than about 1% of the stoichiometric
heated reaction vessel includes a cold chamber, a hot amount of oxygen to completely combust said feed material,
chamber separated from said cold chamber, a reaction and wherein said second amount of free oxygen is less than
tube traversing through said cold and hot chambers; a about 10% of the stoichiometric amount of oxygen to com
primary cyclone, connected to said reaction tube, for 10 pletely combust the carbon contained in said Solid phase
removing ash; and a polishing cyclone, connected to produced in step (a).
said primary cyclone, for removing additional ash; 16. A method of forming syngas, said method comprising
wherein step (b) is performed in the presence of free oxy devolatilizing a carbon-containing feed material to form a gas
gen in an amount between about 0.5% and about 50% of phase and solid phase, wherein said gas phase comprises
the stoichiometric amount of oxygen to completely 15 syngas, wherein said devolatilizing is performed in the pres
combust the carbon contained in said solid phase pro ence of free oxygen in an amount between about 0.5% and
duced in step (a); about 25% of the stoichiometric amount of oxygen to com
wherein the temperature of said heated reaction vessel is pletely combust said feed material, wherein said devolatiliz
controlled to be above the dew point of said gas phase ing includes conveying said carbon-containing feed material
from said devolatilization unit; and through a cascading series of devolatilization chambers,
wherein a portion of said syngas is recycled back to said using augers, at increasing temperatures for Successive
devolatilization unit. devolatilization chambers, and wherein a portion of said Syn
12. The method of claim 11, wherein said amount of free gas is recycled back to the feed to said devolatilization unit.
oxygen is less than about 10% of the stoichiometric amount of 17. The method of claim 16, wherein said devolatilizing is
oxygen to completely combust the carbon contained in said 25 performed in the presence of added steam.
Solid phase produced in step (a). 18. The method of claim 17, wherein said added steam is
13. The method of claim 11, wherein said amount of free present in an amount that is less than about 50% of the
oxygen is between about 10% and about 20% of the stoichio Stoichiometric amount of water to completely convert said
metric amount of oxygen to completely combust the carbon feed material to carbon monoxide and hydrogen.
contained in said solid phase produced in step (a). 30 19. The method of claim 16, wherein said amount of free
14. The method of claim 11, wherein step (a) is performed oxygen is between about 1% and about 10% of the stoichio
in the presence of a first amount of free oxygen that is between metric amount of oxygen to completely combust said feed
about 0.5% and about 10% of the stoichiometric amount of material.
oxygen to completely combust said feed material, and
wherein step (b) is performed in the presence of a second