U.S. patent application number 16/136619 was filed with the patent office on 2019-06-13 for hydrogen utilization and carbon recovery.
The applicant listed for this patent is Cermatec, Inc.. Invention is credited to Singaravelu Elangovan, Mukund Karanijikar.
Application Number | 20190177862 16/136619 |
Document ID | / |
Family ID | 52581635 |
Filed Date | 2019-06-13 |
![](/patent/app/20190177862/US20190177862A1-20190613-C00001.png)
![](/patent/app/20190177862/US20190177862A1-20190613-C00002.png)
![](/patent/app/20190177862/US20190177862A1-20190613-C00003.png)
![](/patent/app/20190177862/US20190177862A1-20190613-C00004.png)
![](/patent/app/20190177862/US20190177862A1-20190613-D00000.png)
![](/patent/app/20190177862/US20190177862A1-20190613-D00001.png)
![](/patent/app/20190177862/US20190177862A1-20190613-D00002.png)
![](/patent/app/20190177862/US20190177862A1-20190613-D00003.png)
![](/patent/app/20190177862/US20190177862A1-20190613-D00004.png)
![](/patent/app/20190177862/US20190177862A1-20190613-D00005.png)
United States Patent
Application |
20190177862 |
Kind Code |
A1 |
Elangovan; Singaravelu ; et
al. |
June 13, 2019 |
HYDROGEN UTILIZATION AND CARBON RECOVERY
Abstract
A method for upgrading bio-mass material is provided. The method
involves electrolytic reduction of the material in an
electrochemical cell having a ceramic, oxygen-ion conducting
membrane, where the membrane includes an electrolyte. One or more
oxygenated or partially-oxygenated compounds are reduced by
applying an electrical potential to the electrochemical cell. A
system for upgrading bio-mass material is also disclosed.
Inventors: |
Elangovan; Singaravelu;
(South Jordan, UT) ; Karanijikar; Mukund; (West
Valley City, UT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Cermatec, Inc. |
Golden |
CO |
US |
|
|
Family ID: |
52581635 |
Appl. No.: |
16/136619 |
Filed: |
September 20, 2018 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
14474843 |
Sep 2, 2014 |
10145020 |
|
|
16136619 |
|
|
|
|
61872184 |
Aug 30, 2013 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25B 11/0463 20130101;
C25B 1/02 20130101; C25B 1/00 20130101; C25B 13/04 20130101; C25B
9/10 20130101; C25B 3/04 20130101 |
International
Class: |
C25B 9/10 20060101
C25B009/10; C25B 1/02 20060101 C25B001/02; C25B 13/04 20060101
C25B013/04; C25B 1/00 20060101 C25B001/00; C25B 3/04 20060101
C25B003/04 |
Goverment Interests
U.S. GOVERNMENT INTEREST
[0002] The Government has rights in this invention pursuant to
Contract No. DE-EE0006288 awarded by the U.S. Department of Energy.
Claims
1. A method for upgrading bio-mass material, the method comprising:
providing an electrochemical cell comprising a ceramic, oxygen ion
conducting membrane; providing bio-mass to the electrochemical
cell, wherein the bio-mass comprises one or more oxygenated or
partially-oxygenated compounds; and passing electrical current
through the electrochemical cell.
2. The method of claim 1, wherein the bio-mass comprises bio-oil
components selected from the group consisting of: carboxylic acids,
ketones, furan derivatives, phenolic compounds, sugars, and
mixtures of the same.
3. The method of claim 1, wherein the bio-mass comprises bio-oil
components selected from the group consisting of: acetic acid,
propanoic acid, 2-butenal, 1-hydroxy-2-propane,
1-hydroxy-2-propanone, 3-hydroxy-2-butanone, 1-hydroxy-2-butanone,
cyclopentanone, 3-furaldehyde, furfural, 2-cyclopenten-1-one,
phenol, 2-cyclopenten-1-one, 2-methyl-2-cyclopentenone,
2-methyl-2-cyclopenten-1-one, o-cresol,
1-hydroxy-2-propanoneacetate, p-cresol, m-cresol,
5-methyl-furfural, 2-hydroxy-3-methyl-2-cyclopenten-1-one,
3-methyl-2-cyclopenten-1-one, 2,4-dimethyl-phenol,
o-methoxy-phenol, 2-methoxy-phenol, 2-furanone, 4-ethyl-phenol,
3-ethyl-phenol, 5-methyl-2-furanone, 1,2-benzenediol,
3-methyl-2-furanone, 6-ethyl-o-cresol, 2-methoxy-4-methyl-phenol,
4-methyl-guaiacol, 3-methyl-1,2-benzenediol,
4-methyl-1,2-benzenediol, p-ethyl-guaiacol,
4-methyl-5H-furan-2-one, 4-(2-propenyl)-phenol,
2,5-dimethyl-1,4-benzenediol, 4-ethyl-1,2-benzenediol,
2-methoxy-4-(2-propenyl)-phenol, d-mannose, eugenol,
4-propyl-1,3-benzenediol, 2-methoxy-5-(1-propenyl)phenol,
2-methoxy-4-propenyl-phenol, vanilin,
4-hydroxy-3-mehoxy-benzaldehyde, 4-chromanol,
2-methoxy-4-propyl-phenol, Apocynin, Anhydro-d-mannosan,
1-(4-hydroxy-3-methoxyphenyl)-ethanone, guaiacylacetone, and,
1,2-ethoxy-6-(methoxy methyl)-phenol, and mixtures of the same.
4. The method of claim 1, further comprising heating the bio-mass
to a temperature between about 400.degree. C. to about 1000.degree.
C.
5. The method of claim 1, further comprising removing oxygen gas
from the electrochemical cell.
6. The method of claim 1, wherein the electrochemical cell is
operated substantially free of hydrogen gas.
7. The method of claim 1: wherein the electrochemical cell
comprises a cathode, an anode, and the ceramic, oxygen-ion
conducting membrane comprises an electrolyte; the method further
comprising: contacting the bio-mass with the cathode; applying an
electric potential between the cathode and the anode; and heating
the bio-mass.
8. The method of claim 7, wherein the electrolyte comprises
zirconia doped with one or more trivalent cations selected from the
group consisting of: yttria, scandia, ytterbia, and combinations
thereof.
9. The method of claim 7, wherein the electrolyte comprises ceria
doped with one or more trivalent cations selected from the group
consisting of: yttria, samaria, gadolinia, and combinations
thereof.
10. The method of claim 7, wherein the electrolyte comprises
strontium and magnesium doped lanthanum gallate.
11. The method of claim 7, wherein the bio-mass is heated to a
temperature between about 400.degree. C. to about 1000.degree.
C.
12. The method of claim 7, further comprising generating steam that
contacts the cathode thereby ionizing the steam and producing
reactive hydrogen.
13. The method of claim 12, wherein the steam is generated by
heating the biomass.
14. The method of claim 12, wherein the hydrogen reacts with
hydrocarbon ions formed in the electrochemical cell thereby
producing one or more hydrocarbon compounds.
15.-21. (canceled)
22. A method for electrolytic reduction of bio-mass material, the
method comprising: generating bio-mass vapor from bio-mass material
using a pyrolyzer; transporting the bio-mass vapor from the
pyrolyzer to an electrochemical deoxygenation unit in fluid
communication with the pyrolyzer, the electrochemical deoxygenation
unit comprising at least one electrochemical cell comprising at
least one ceramic, oxygen-ion conducting membrane; and passing
electrical current through the at least one electrochemical cell to
deoxygenate hydrocarbon compounds in the bio-mass vapor.
23. The method of claim 22, wherein the method further comprises
transporting the bio-mass material from a bio-mass container to the
pyrolyzer, wherein the bio-mass material comprises one or more
oxygenated or partially-oxygenated hydrocarbon compounds.
24. The method of claim 22, wherein the method further comprises
collecting oxygen from the deoxygenated hydrocarbon compounds in an
oxygen vessel coupled to the electrochemical deoxygenation unit via
an oxygen conveyance outlet.
25. The method of claim 22, wherein the method further comprises
transporting hydrocarbon vapors from the electrochemical
deoxygenation unit to a condenser to condense the hydrocarbon
vapors into a mixture of hydrocarbon gases and liquids, the
electrochemical deoxygenation unit coupled to the condenser via a
hydrocarbon conveyance outlet.
26. The method of claim 25, wherein the at least one
electrochemical cell further comprises: an anode configured for
residing in an oxidizing environment; a cathode comprising a first
surface and a second surface; a fluid conduit adjacent to a first
surface of the cathode, the fluid conduit adapted to facilitate
contact between the bio-mass vapor and the first surface of the
cathode; a power source that applies electrical potential between
the cathode and the anode; and wherein the at least one ceramic,
oxygen-ion conducting membrane is positioned between the second
surface of the cathode and the anode, whereby the fluid conduit and
the at least one ceramic, oxygen-permeable membrane are configured
such that the bio-mass vapor is not in contact with the anode.
27. The method of claim 22, wherein the electrochemical cell is
operated substantially free of hydrogen gas.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 14/474,843, filed Sep. 2, 2014, which claims priority to
U.S. Provisional Application Ser. No. 61/872,184, filed Aug. 30,
2013. The contents of each of the above applications are
incorporated herein by reference for all purposes.
FIELD OF THE INVENTION
[0003] The present disclosure relates generally to methods and
systems for increasing energy density in bio-mass material. More
particularly, the present disclosure relates to pyrolysis methods
for enriching bio-mass material.
BACKGROUND OF THE INVENTION
[0004] Rapid thermal decomposition (pyrolysis) in the absence of
oxygen is a process to extract hydrocarbon liquid from woody
bio-mass as a protentional petroleum substitute. Pyrolysis oil,
also known as bio-oil, has properties such as low heating value,
incomplete volatility, acidity, instability, and incompatibility
and standard petroleum fuels that significantly restrict its
application. The undesirable properties of pyrolysis oil result
from the chemical composition of bio-oil that mostly consists of
different classes of oxygenated organic compounds.
[0005] The elimination of oxygen is thus necessary to transform
bio-oil into a liquid fuel that would be accepted as transportation
fuel and economically attractive. Two types of processes are
generally used to remove oxygen from organic molecules: catalytic
cracking and hydrotreating.
[0006] Catalytic cracking removes oxygen in the form of water and
carbon oxides using shape-selective catalysts. Catalytic cracking
accomplishes deoxygenation through simultaneous dehydration,
decarboxylation, and decarbonylation reactions occurring in the
presence of catalysts. In the past, zeolite such as ZSM5 catalysts
has been used to perform cracking. Other catalysts such as
molecular sieves (SAPOs), mordenite and HY-zeolite have also been
utilized. The extent of coking (8-25%), high extent of formation of
light ends (gas-phase hydrocarbons) and low quality of final fuel
grade products are prohibitive towards a scalable cracking process.
All these factors result in carbon and hydrogen loss thereby
reducing both carbon and hydrogen efficiencies.
[0007] Hydrodeoxygenation ("HDO") is considered the leading
technology to achieve oxygen removal from bio-oil. HDO also known
as hydrotreating involves high-temperature, high-pressure
processing in the presence of hydrogen and catalyst to remove
oxygen in the form of water. HDO consists of contracting bio-oil
with hydrogen at high pressure and high temperature in presence of
catalyst. Both of these processes require new equipment wherein the
capital expenditure is significantly higher. Moreover, the catalyst
is susceptible to sulfur and phosphorus impurities in bio-mass.
Most of the catalysts used for hydrodeoxygenation are some
variations of Co--Mo or Ni--Mo impregnated on a support. Many
investigators have focused upon alumina as a preferred catalyst
support. Others have investigated carbon, silica and zeolite based
supports.
[0008] However, HDO suffers from significant challenges, including:
1) coking, which limits the catalyst lifetime; 2) polymerization of
various compounds in bio-oil before deoxygenation due to sequential
nature of bio-oil productions and catalytic treatment; 3)
deactivation of HDO catalysts by the presence of water in the
pyrolysis oil (deactivation occurs by leaching sulfur from active
sites since these catalysts are usually sulfide prior to HDO
process to alleviate coking); 4) hydrothermally unstable nature of
zeolite based catalysts compared to noble metal catalysts, which
are cost prohibitive, 5) requirement of significant quantities of
hydrogen to remove oxygen (cost of hydrogen is approximately $1.50
per gallon of product hydrocarbon); 6) economic availability of
hydrogen at distributed smaller scale suitable for bio-mass
conversion; and 7) significant process exotherm due to high oxygen
removal requirement (25% by mass), which consequentially requires
high recycle rates at commercial scale to manager the heat, thereby
contributing to high processing costs.
[0009] Thus, there are numerous challenges that prevent
commercialization of bio-oil upgrading to hydrocarbons process. An
alternative economically feasible, hydrogen independent and
decentralized process is needed to convert bio-mass derived
pyrolysis oil to refinery ready hydrocarbons with an increased
energy density.
SUMMARY OF THE INVENTION
[0010] Methods and systems for increasing energy density in
bio-mass material are disclosed.
[0011] In one aspect, a method for upgrading bio-mass material
includes providing an electrochemical cell that includes a ceramic,
oxygen-permeable membrane. The method also includes providing
bio-mass to the electrochemical cell. The bio-mass includes one or
more oxygenated or partially-oxygenated compounds. The method also
includes passing electrical current through the electrochemical
cell.
[0012] In another aspect, a method for increasing energy density in
bio-mass material includes providing an electrochemical cell
including a cathode, an anode, and a ceramic, oxygen-ion conducting
membrane. The ceramic, oxygen-ion conducting membrane includes an
electrolyte. The method also includes contacting bio-mass with the
cathode. The bio-mass includes one or more oxygenated or
partially-oxygenated compounds. The method also includes applying
an electric potential between the cathode and the anode. The method
also includes heating the bio-mass.
[0013] In another aspect, a system for upgrading bio-mass material
in an electrolytic cell includes a cathode in contact with
bio-mass. The bio-mass includes one or more oxygenated or
partially-oxygenated compounds. The system also includes an anode.
The system also includes a ceramic, oxygen-ion conducting membrane
located between the cathode and anode. The system also includes a
power source that applies an electric potential between the cathode
and anode.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a schematic diagram illustrating a means of
removing oxygen from bio-mass material, according to one
embodiment.
[0015] FIG. 2 is a cross-sectional view of an electrochemical cell
illustrating the removal of oxygen from bio-mass material,
according to one embodiment.
[0016] FIG. 3 is a cross-sectional view of an electrochemical cell
utilizing an electric potential to remove oxygen from bio-mass
material, according to one embodiment.
[0017] FIG. 4 is a perspective view of an electrochemical cell for
removing oxygen from bio-mass material, according to one
embodiment.
[0018] FIG. 5 is a schematic diagram illustrating the incorporation
of the system in a hydrocarbon production facility, according to
one embodiment.
DETAILED DESCRIPTION
[0019] Methods and systems of synergistically converting
lignocellulosic bio-mass and electricity to energy dense liquid
fuels are disclosed. Because bio-mass materials typically have
relatively low energy density, it is hard to transport the
materials for fuel needs. Moreover, many of the bio mass materials
include chemical functional groups, like carboxylic acids, which
result in gelation, thereby complicating material handling and
storage. For example, many of the materials, when stored, turn into
gels that can be difficult to process and transport. In additional,
electricity is difficult to store for use at sites where bio-mass
material is harvested or otherwise collected. This prevents
increased utilization of renewable electrical sources such as solar
or wind. Furthermore, delivering hydrogen to dispersed bio-mass
collection sites is prohibitively expensive.
[0020] According to some embodiments, a method is disclosed that
increases energy density in bio-mass material, thereby making it
easier to transport for fuel needs. In some embodiments, the system
may be integrated with renewable electricity sources, thereby
amplifying the energy in bio-mass material with renewable
energy.
[0021] Additionally, in some embodiments, the removal of oxygen
from bio-mass material stabilizes the material for transport.
According to same embodiments, the system and process produce a
product that lacks the acidity problems typical of pyrolysis oil in
some embodiments, the carbon and hydrogen efficiency of the process
is considerably higher than the HDO method. The process can be
integrated directly with a pyrolyzer. In some embodiments, the
overall system operates atmospheric pressure, thereby obviating the
need for expensive pressure vessels.
[0022] According to some embodiments, the method for upgrading
bio-mass provides an efficient electrochemical deoxygenation
("EDOx") technology with the potential to economically convert
oxygenated oils and/or gases to a mixture of hydrocarbon products
suitable for subsequent fractionation in conventional refineries.
In one embodiment of an EDOx unit, the EDOx process removes oxygen
aging electrons (provided via electricity) stoichiometrically. In
one embodiment, the EDOx process is carried out in an oxygen ion
transport dense ceramic membrane reactor that selectively removes
oxygen as a gas. Modularity of both the fast pyrolyzer and EDOx
unit in some embodiments allows a smaller integrated facility to be
economically attractive, thereby increasing both the flexibility
for deployment and broadening the potential customer base.
[0023] The systems and methods for increasing energy density in
bio-mass material provide numerous advantages. For example, the
system can be operated substantially free from the need to supply
elemental hydrogen. Alternatively, hydrogen can be supplied in
reduced amounts compared to conventional techniques. For example,
cogeneration facilities using renewable sources and/or existing
infrastructure provide electricity or hydrogen gas.
[0024] In some embodiments, oxygen gas generated by the
electrolysis can be selectively removed as a pure gas. The removal
of the oxygen from the pyrolyzed material stabilizes the
hydrocarbon product for transport. The EDOx process produces a
product with none of the acidity problems typical of pyrolysis oil.
In one embodiment, the EDOx process is theoretically 100% carbon
and hydrogen efficient because oxygen is removed as O.sub.2 (g). If
char production is minimized during pyrolysis, the entire system
can achieve such atom efficiencies. In one embodiment, the EDOx.
process is integrated directly with a pyrolyzer. Thus, the overall
system can operate at atmospheric pressure, thereby obviating the
need for expensive pressure vessels. In one embodiment, modularity
of both the fast pyrolyzer and EDOx unit allows a smaller
integrated facility to be economically attractive, thereby
increasing both the flexibility for deployment and broadening the
potential customer base. In one embodiment, oxygen can be recovered
as a by-product, which aids in overall process economics. The
working principle of the EDOx process is similar to steam
electrolysis to produce hydrogen or co-electrolysis of steam and
carbon dioxide to produce syngas.
[0025] In one aspect, a system for upgrading bio-mass material in
an electrolytic cell includes a cathode in contact with bio-mass,
an anode, a ceramic, oxygen-ion conducting membrane located between
the cathode and anode, and a power source that applies an electric
potential between the cathode and anode.
[0026] In one embodiment, the bio-mass includes one or more
oxygenated or partially-oxygenated compounds. The bio-mass may
include bio-oil components including carboxylic acids, ketones,
furan derivatives, phenolic compounds, and sugars. The bio-mass may
include bio-oil components including one or more of the following:
acetic acid, propanoic acid, 2-butenal, 1-hydroxy-2-propane,
1-hydroxy-2-propanone, 3-hydroxy-2-butanone, 1-hydroxy-2-butanone,
cyclopentanone, 3-furaldehyde, furfural, 2-cyclopenten-1-one,
phenol, 2-cyclopenten-1-one, 2-methyl-2-cyclopentenone,
2-methyl-2-cyclopenten-1-one, o-cresol,
1-hydroxy-2-propanone-acetate, p-cresol, m-cresol,
5-methyl-furfural, 2-hydroxy-3-methyl-2-cyclopenten-1-one,
3-methyl-2-cyclopenten-1-one, 2,4-dimethyl-phenol,
o-methoxy-phenol, 2-methoxy-phenol, 2-furanone, 4-ethyl-phenol,
3-ethyl-phenol, 5-methyl-2-furanone, 1,2 benzenediol,
3-methyl-2-furanone, 6-ethyl-o-cresol, 2-methoxy-4-methyl-phenol,
4-methyl-guaiacol, 3-methyl-1, 2-benzenediol, 4-methyl-1,
2-benzenediol, p-ethyl-guaiacol, 4-methyl-5H-furan-2-one,
4-(2-propenyl)-phenol, 2,5-dimethyl-1,4-benzenediol, 4-ethyl-1,
2-benzenediol, 2-methoxy-4-(2-propenyl)-phenol, d-mannose, eugenol,
4-propyl-1,3-benzenediol, 2-methoxy-5-(1-propenyl)-phenol,
2-methoxy-4-propenyl-phenol, vanillin,
4-hydroxy-3-mehoxy-benzaldehyde, 4-chromanol,
2-methoxy-4-propyl-phenol, Apocynin, Anhydro-d-mannosan,
1-(4-hydroxy-3-methoxyphenyl)-ethanone, guaiacylacetone, and
1,2-ethoxy-6-(methoxy methyl)-phenol, and mixtures of the same.
[0027] In one embodiment, the anode is an air electrode. In one
embodiment, the anode is a lanthanum-strontium-manganite ("LSM")
electrode. In one embodiment, the anode is an oxygen electrode.
Suitable oxygen electrodes include electronic conducting ceramic
materials such as doped lanthanum manganite, lanthanum cobaltite,
or oxygen ion-electron mixed conducting ceramic materials such as
doped lanthanum cobalt ferrite, or other suitable ceramics
belonging to the family of perovskites, pyrochlore and others. The
anode may include one or more of the following: doped lanthanum
manganite, doped lanthanum cobaltite, doped lanthanum cobalt
ferrite, electron conducting ceramics belonging to the family of
perovskites or pyrochlores, oxygen ion-electron conducting ceramics
belonging to the family of perovskites or pyrochlores, nickel-doped
zirconia, nickel-doped ceria, nickel, cobalt, molybdenum,
ruthenium, platinum, praseodymium, cerium, other elements from the
rare earth element group or from the precious metal group, or
combinations thereof.
[0028] In one embodiment, the anode is a doped lanthanum manganite,
doped lanthanum cobaltite, doped lanthanum cobalt ferrite, electron
conducing ceramics belonging to the family perovskites or
pyrochlores, oxygen ion-electron conducting ceramics belonging to
the family of perovskites or pyrochlores, oxygen ion-electron
conducting ceramics belonging to the family of perovskites or
pyrochlores, or combinations thereof. In one embodiment, the anode
is cobalt-ferrite perovskite.
[0029] In one embodiment, the cathode is sulfur tolerant based on a
modified Ni-ceria composite. In one embodiment, the cathode is
sulfur tolerant up to about 100 s of ppm H.sub.2S and is coke
resistant to gaseous hydrocarbons. The cathode may include Cu or
Cu--Ni as a coating material on the metal interconnect. The coating
material can provide additional coke and sulfur tolerance in the
presence of higher hydrocarbons and oxygenates that may be present
in the bio-oil.
[0030] In one embodiment, the cathode is a fuel (bio-oil) side
electrode. Fuel (bio-oil) side electrodes could be a mixture of
ceramics and metal (cermet). Examples include nickel-doped
zirconia, nickel-doped ceria. The metal can be a mixture (for
example an alloy) of metals such as nickel-copper or a
substantially pure metal such as copper. The fuel side electrode
may also contain catalyst particles such as Ni, Co, Mo, Ru, Pt, Pr,
Re, Ce or any catalyst particles from the rare earth element group
or precious metal group. The fuel side electrode can include a
combination of catalyst particles to provide catalytic functions.
Examples of combinations include Co--Mo, Ni--Mo, Ni--W and other
combinations to provide catalytic functions. In another embodiment
the catalyst particles may be sulfided, carbided or phosphided.
Examples include MoS, Mo.sub.2C, MoP, Ni.sub.2P, WP, and CoP. In
another embodiment, the fuel-side electrode is only made of
ceramic. Examples of ceramic fuel-side electrode include strontium
titanate, doped ceria, doped lanthanum chromite and the like. In
one embodiment, the fuel-side electrode is based at least partially
on the composition of bio-mass material and the tendency to coke.
Some electrodes, for example all ceramic or Cu containing ones,
show less tendency to coke.
[0031] The cathode may include one or more of the following doped
lanthanum manganite, doped lanthanum cobaltite, doped lanthanum
cobalt ferrite, oxygen ion-electron conducting ceramics belonging
to the family of perovskites or pyrchlores, nickel-doped zirconia,
nickel-doped ceria, nickel, cobalt, molybdenum, ruthenium,
platinum, praseodymium, cerium, other elements from the rare earth
element group or from the precious metal group, or combinations
thereof. In one embodiment, the cathode includes nickel-doped
zirconia, nickel-doped ceria, nickel, cobalt, molybdenum,
ruthenium, platinum, praseodymium, cerium, other elements from the
rare earth element group or from the precious metal group or
combinations thereof. In one embodiment, the cathode includes
nickel-ceria.
[0032] In one embodiment, the system also includes an electrolyte
or an electrolytic layer. In one embodiment, the electrolyte or
electrolytic layer is located between the cathode and anode. In one
embodiment, the system uses any high temperature oxygen ion
conducting electrolyte. In one embodiment, the electrolyte or
electrolytic layer is at least partially made of zirconia doped
with trivalent cations. The trivalent cations may include yttria,
scandia, ytterbia. In one embodiment, the electrolyte or
electrolytic layer is zirconia doped with yttria, scandia,
ytterbia, and the like or combinations thereof. In one embodiment,
the electrolyte or electrolytic layer includes scandium-doped
zirconia. In one embodiment, the electrolyte or electrolytic layer
includes ceria doped with trivalent cations. The trivalent cations
may include yttria, samaria, gadolinia. In one embodiment, the
electrolyte or electrolytic layer is strontium and magnesium doped
lanthanum gallate.
[0033] In one embodiment, the system includes a means for heating
the electrolytic cell to a temperature between about 400.degree. C.
to about 1000.degree. C. In another embodiment, the system includes
a means for heating the electrolytic cell to a temperature between
about 500.degree. C. to about 800.degree. C. The system may include
a heater such as a natural gas burner. In one embodiment, the
system is heated with the hydrocarbon gases separated from the
hydrocarbon vapors following the EDOx process. The char produced in
the pyrolysis process may be combusted to provide the heat for the
system. The sensible heat of the bio-oil vapor may be used to heat
the EDOx unit.
[0034] In one embodiment, the system can economically convert
oxygenated oils and/or vapors to a mixture of hydrocarbon products
suitable for subsequent fractionation in conventional
[0035] FIG. 1 shows a schematic system for increasing energy
density in bio-mass material, according to one embodiment. As
depicted, bio-mass undergoes pyrolysis. The solid co-products may
then be used in utility applications. The non-solid co-products may
then undergo electro-catalytic deoxygenation. In some embodiments,
electro-catalytic deoxygenation produces one or more of the
following by products: oxygen gas, liquid hydrocarbons, and fuel
gas co-products. The fuel gas co-products may be used in utility
applications.
[0036] In some embodiments, the bio-mass oil can be cooled to
separate the aqueous and non-aqueous phases and separately heated
to EDOx suitable temperature to deoxygenate the compounds. In one
embodiment, deoxygenation is performed without cooling.
[0037] In another aspect, a method for upgrading bio-mass material
is disclosed. The method includes the step of providing an
electrochemical cell that has a ceramic, oxygen-ion conducting
membrane. The membrane is sandwiched between two electrodes, an
anode and a cathode. Optionally, the method for upgrading bio-mass
may utilize aspects of the electrodes of the types described in
U.S. Pat. Nos. 8,354,011 and 7,976,686, both patents hereby
incorporated by reference in their entireties.
[0038] Bio-mass is then provided to that electrochemical cell. The
bio-mass includes one or more oxygenated or partially-oxygenated
compounds. An electrical potential or current is then applied to
the cell. The degree of upgrading of the bio-mass material may be
modulated by the amount of electric potential applied through the
electrochemical cell. In one embodiment, the method also includes
the step of heating the bio-mass. In one embodiment, the method
also includes the step of removing oxygen gas from the cell.
[0039] The electric current can come from a variety of sources. In
one embodiment, the electricity and/or electric current is obtained
from cogeneration facilities and/or existing infrastructure.
Similar to steam electrolysis, the method can be nearly 100%
efficient electrically, i.e., nearly all electrical energy is
captured in the heating value of deoxygenated bio-oil and gaseous
hydrocarbon.
[0040] In one embodiment, the electrochemical cell is operated
substantially free of hydrogen gas. In one embodiment, the
electrochemical cell excludes the use of an external hydrogen
source. In one embodiment, the electrochemical cell is operated
free of any hydrogen gas.
[0041] In one embodiment, the bio-mass is heated to a temperature
between about 400.degree. C. to 1000.degree. C. The bio-mass may be
heated to a temperature between about 500.degree. C. to about
800.degree. C. In another embodiment, the bio-mass is heated to a
temperature of about 400.degree. C. The bio-mass may be heated to a
temperature of about 500.degree. C. In one embodiment, the bio-mass
is heated to a temperature of about 600.degree. C. The bio-mass may
be heated to a temperature of about 700.degree. C. In one
embodiment, the bio-mass is heated to a temperature of about
800.degree. C. In another embodiment, the bio-mass is heated to a
temperature of about 900.degree. C. The bio-mass may be heated to a
temperature of about 1000.degree. C.
[0042] In another aspect, a method for increasing energy density in
bio-mass material is disclosed. The method includes the step of
providing an electrochemical cell. In one embodiment, the
electrochemical cell includes a ceramic, oxygen-ion conducting
membrane, a cathode, and an anode. In one embodiment, only oxygen
ions pass through the membrane. In one embodiment, the method also
includes the step of contacting bio-mass with the cathode. In one
embodiment, the method also includes one or more oxygenated or
partially-oxygenated compounds. In one embodiment, the method also
includes the step of applying an electric potential between the
cathode and the anode.
[0043] In one embodiment, the method also includes the step of
heating the bio-mass. In one embodiment, the bio-mass is heated to
a temperature that reduces the degree of oxygenation of the
bio-mass.
[0044] In one embodiment, multiple electrochemical cells each
including cathode, electrolyte, and anode are separated by an
interconnect material. In one embodiment, each cell is separated by
an interconnect material made of metal or ceramic or combinations
thereof. Examples of interconnect material include stainless steel,
super alloys, electrically conducting ceramic oxides such as doped
lanthanum chromite.
[0045] In one embodiment, the electrolyte is located between the
anode and the cathode. In one embodiment, the electrolyte includes
zirconia doped with one or more trivalent cations selected from the
group consisting of: yttria, scandia, ytterbia, and combinations
thereof. In one embodiment, the electrolyte includes ceria doped
with one or more trivalent cations selected from the group
consisting of: yttria, ytterbia, samaria, gadolinia, and
combinations thereof. In one embodiment, the electrolyte includes
lanthanum gallate doped with strontia and magnesia.
[0046] In one embodiment, the bio-mass is heated to a temperature
that activates the bio-mass. The electricity may then split the
bio-mass to produce oxygen ions and hydrocarbon tons. In one
embodiment, the oxygen ions from bio-mass splitting is transported
across the ionic membrane. According to some embodiments, the
method also includes the step of heating water at the cathode to a
temperature that vaporizes the water. In some embodiments, the
method also includes the step of generating steam that contacts the
cathode thereby ionizing the steam and producing reactive hydrogen.
The ionization of the steam produces reactive hydrogen. The
electricity splits water at high temperature. The oxygen from the
water splitting is transported across the ionic membrane,
[0047] In one embodiment, the reactive hydrogen from the water
splitting deoxygenates the oxygenated compounds of the bio-mass
material. In one embodiment, the reactive hydrogen reacts with
hydrocarbon ions in the electrochemical cell to form one or more
hydrocarbon compounds. In one embodiment, the bio-mass and water
are heated simultaneously. In another embodiment, the bio-mass and
water are heated at different times. In one embodiment, one
hydrocarbon ion can combine with other similar ions or fragments to
form one or more dimers or other complex hydrocarbons that have
potentially reduced oxygen content. The type of hydrocarbon formed
depends on one or more of the following: the catalytic properties
of the cathode, the type of oxygenated compound, and cell
temperature.
[0048] In one embodiment, about 20% to about 40% of oxygen is
recovered as a by-product from the bio-mass material. In another
embodiment, more than 20% of oxygen is recovered as a by-product
from the bio-mass material. In one embodiment, about 30% of oxygen
is recovered as a by-product from the bio-mass material. In one
embodiment, about 30% of oxygen is recovered as a by-product from
the bio-mass material. In another embodiment, about 40% of oxygen
is recovered as a by-product from the bio-mass material.
[0049] In one embodiment, the number of oxygen atoms in the
bio-mass material is reduced by one or more oxygen atoms following
the step of heating the bio-mass and applying electric potential to
the electrochemical cell. In one embodiment, there are no oxygen
atoms remaining in the bio-mass material following the step of
heating the bio-mass and applying electric potential to the
electrochemical cell. In one embodiment, the number of oxygen atoms
of one or more bio-mass components is reduced by one or more oxygen
atoms following the step of heating the bio-mass material and
applying electric potential to the electrochemical cell. In one
embodiment, there are no oxygen atoms remaining in one or more
bio-mass components following the step of heating the bio-mass
material and applying electric potential to the electrochemical
cell.
[0050] FIG. 2 is a cross-sectional view of an electrochemical cell
illustrating the removal of oxygen from bio-mass material,
according to one embodiment. As shown in FIG. 2, electrochemical
cell 200 includes cathode 202, anode 204, and electrolyte 206. In
the embodiment of FIG. 2, electrolyte 204 is located between
cathode 202 and anode 206. FIG. 2 shows the direct deoxygenation of
the oxygenated compound on the surface of cathode 202. The oxygen
ions removed at the surface of cathode 202 are transported from
cathode 202, across electrolyte 206, and to anode 204. The oxygen
leaves electrochemical cell 200 in the form of oxygen gas.
Electrochemical cell 200 of FIG. 2 includes front end 208 and back
end 210. In one embodiment, the oxygen gas that is released from
electrochemical cell flows in a direction from front end 208 to
back end 210. As shown in FIG. 2, in some embodiments, the process
removes all oxygen atoms from the oxygenated compound. In other
embodiments, the process partially removes the number of oxygen
atoms.
[0051] In one embodiment, the method includes the step of removing
oxygen from bio-mass material using stoichiometric electrons
(provided via electricity). In one embodiment, the method is
carried out in an oxygen ion transporting dense ceramic membrane
reactor that selectively removes oxygen as a pure gas. In one
embodiment, the membrane only removes oxygen as a gas. In one
embodiment, the membrane only removes oxygen as a pure gas.
[0052] In one embodiment, the oxygen from the oxygenated or
partially-oxygenated compound may be directly removed through the
electrochemical process or indirectly by reaction with the hydrogen
produced from electrolyzing (i.e., removing oxygen from) steam that
is present. This is similar to the co-electrolysis (simultaneous
electrolysis of CO.sub.2 and H.sub.2O) process. Optionally, the
method for upgrading bio-mass may utilize aspects of the
electrolysis processes and systems described in U.S. Pat. Nos.
8,075,746 and 7,951,283, both patents hereby incorporated by
reference in their entireties.
[0053] In one embodiment, high temperature electrolysis using solid
oxide electrolyte cells is used to generate high purity hydrogen.
Co-electrolysis is fundamentally a variation of high temperature
steam electrolysis. In one embodiment, an electrical potential is
applied across a gas tight and electrically insulating ceramic
membrane, having a high conductivity of oxygen ions.
[0054] Zirconia (ZrO.sub.2), doped with tri-valent cations (e.g.,
Y.sub.2O.sub.3 to 8 mole %) may be used to stabilize a cubic
structure and introduce oxygen vacancy defects. If the potential is
greater than the free energy of formation, corrected for local
reactant and product partial pressures, an H.sub.2O or CO.sub.2
molecule will decompose as one oxygen atom is transported across
the membrane in the form an oxygen ion (O.sup.=) leaving behind
hydrogen or carbon monoxide. However, quantitative analysis of
co-electrolysis is significantly more complex than simple steam
electrolysis. This is primarily due to the multiple, interacting
reactions that occur: steam electrolysis, CO.sub.2 electrolysis,
and the reverse shift reaction (RSR), as shown in Formula 1:
CO.sub.2+H.sub.2CO+H.sub.2O Formula 1
[0055] Reaction kinetics govern the relative contributions of these
three reactions. It is also important to note that the electrolysis
reactions are not equilibrium reactions. In some embodiments, the
electrolyte separates the products from the reactants. However, the
RSR is a kinetically fast, near equilibrium reaction at high
temperature in the presence of a Ni catalyst. In one embodiment,
the electrolysis cell cathode includes a nickel ceramic composite
and an effective shift or reforming catalyst. In one embodiment,
all four species participating in the RSR are present on the
cathode, as shown in FIG. 3.
[0056] A similar process scheme can be envisioned for deoxygenation
of bio-mass oil vapor. Similar to electrolysis of CO.sub.2, oxygen
can be extracted directly from an oxygenated compound by
application of electric potential across a solid oxide cell, or
from steam (H.sub.2O molecule), which in turn produces
hydrogen.
[0057] FIG. 3 is a cross-sectional view of an of an electrochemical
cell utilizing electricity to remove oxygen from bio-mass material,
according to one embodiment. As shown in FIG. 3, electrochemical
cell 300 includes cathode 302, anode 306, and electrolyte 304. In
the embodiment of FIG. 3, electrolyte 304 is located between
cathode 302 and anode 306. FIG. 3 shows the direct deoxygenation of
art oxygenated compound on the surface of cathode 302 when power
source 312 provides an electric potential between cathode 302 and
anode 306. In one embodiment, the oxygen ions removed at the
surface of cathode 302 are transported from cathode 302, across
electrolyte 304, and to anode 306. The oxygen leaves
electrochemical cell 300 in the form of oxygen gas. Electrochemical
cell 300 of FIG. 3 includes front end 308 and back end 310. In one
embodiment, the oxygen gas that is released from electrochemical
cell flows in a direction from front end 308 to back end 310. In
one embodiment, the oxygen gas is collected as a by-product.
[0058] In FIG. 3, the application of electric potential results in
the ionization of steam at cathode 301, thereby producing oxygen
ions and hydrogen. The oxygen from the water splitting is
transported across the membrane of electrochemical cell 300. The
hydrogen from the water splitting deoxygenates the oxygenated
compounds of the bio-mass material. The hydrogen reacts with the
hydrocarbon ions to form one or more hydrocarbon compounds. The
hydrogen produced from the water splitting reacts with oxygenated
compounds to produce lower oxygenates or even hydrocarbons and
water.
[0059] In one embodiment, the extent of reduction is determined by
one or more of the following: the hydrogen partial pressure,
temperature, and electric current generated by the applied voltage.
Table 1 shows the kinds of reactions that can happen in the cathode
chamber by hydrogen reduction of pyrolysis vapor resulting in
hydrocarbons.
[0060] A typical and analogous reactions of bio-oil components are
shown in Table 1. Other equivalent reactions may also occur in
other embodiments. In all reactions, as stated above, H.sub.2 may
be provided from electrolysis of steam present in the bio-oil or
direct electrochemical ionization of oxygen and transport of oxygen
ion through the membrane.
TABLE-US-00001 TABLE 1 Hydrocarbons from Pyrolysis Oil Acids
R--COOH + 3H.sub.2 .fwdarw. RCH.sub.3 + 2H.sub.2O Acids 2R--COOH
.fwdarw. R--R + 2CO.sub.2 Aldehydes R--CHO + 2H.sub.2 .fwdarw.
R--CH.sub.3 + H.sub.2O Aldehydes 2R--CHO + 3H.sub.2 .fwdarw.
R--CH.sub.2--CH.sub.2--R + 2H.sub.2O Ketones R--CO--R + 2H.sub.2
.fwdarw. R.sub.2CH.sub.2 + H.sub.2O Ketones 2R--CO--R' + 3H.sub.2
.fwdarw. RR'CH--CHR'R + 2H.sub.2O Alcohols R--CH.sub.2OH + H.sub.2
.fwdarw. R--CH.sub.3 + H.sub.2O Ethers ##STR00001## ##STR00002##
Phenols ##STR00003## ##STR00004##
[0061] FIG. 4 shows electrochemical button cell 400, according to
one embodiment. Electrochemical button cell 400 is a solid oxide
electrolysis button cell with about 2 cm.sup.2 electrode area is
used, at about 650.degree. C. The temperature of electrochemical
button cell 400 is measured with thermocouple 407.
[0062] Electrochemical button cell 400 consists of Sc-doped
zirconia electrolyte 403, cobalt-ferrite perovskite anode 401, and
nickel-ceria composite cathode (not shown). The ceria-composite
cathode is located on the interior side of alumina tube 413.
Electrochemical button cell 400 also includes reference electrode
411.
[0063] In one embodiment, acetone is used as the oxygenated
hydrocarbon. Protons or hydrogen generated from steam electrolysis
can be used to hydrodeoxygenate acetone to yield similar products.
In one embodiment, the process may include a combination of
both.
[0064] In one embodiment, acetone vapor, steam, and hydrogen are
provided to electrochemical button cell 400 through alumina tube
413. According to the embodiment of FIG. 4, electrochemical button
cell 400 is manifolded on the cathode side so that vapors of the
bio-mass can be fed to the cathode through alumina tube 413. In
FIG. 4, anode 401 where oxygen, transported from the oxygenated
bio-oil compound and steam in the feed, is evolved is open to
ambient air. In one embodiment, oxygen is collected as a
by-product.
[0065] According to FIG. 4, electrochemical button cell 400 also
includes platinum mesh current distributor 405 that is attached to
the cathode. In another embodiment, the electrochemical button cell
includes a current collector attached to the cathode. In one
embodiment, a platinum mesh current collector or a nickel mesh
current collector is attached to the cathode. In FIG. 4, platinum
mesh current distributor 405 is attached to power lead wire 409.
Multiple leads may be attached to each of the platinum mesh and
some may be used to measure cell voltage and others to measure
current through the cell. Support structure 415 may be used to
secure one or more power lead wire 409. In FIG. 4, support
structure 415 consists of flexible wire that holds power lead wire
409 in place.
[0066] In one embodiment, the system and process may convert an
acetone and water mixture to propane using electricity. The
electricity splits water at high temperature wherein the produced
hydrogen removes the oxygen. The oxygen from water splitting is
transported across the ionic membrane.
[0067] Due to varying vapor pressures of acetone and water, two
separate feed systems may be used: a water bath at about 82.degree.
C. through which hydrogen gas is bubbled, and an acetone bath at
about ambient temperature through which nitrogen gas is bubbled. In
one embodiment, the two streams are mixed and fed into the cathode
chamber using alumina tube 407.
[0068] As the nickel in the cathode of FIG. 4 is likely to be a
chemical catalyst, the outlet gas composition is measured both at
no current (open circuit voltage, OCV). and under a current of
about 100 mA. Analysis can be done using two separate gas
chromatographs (HP 7890 and Agilent microGC) so that concentrations
of permanent gases and hydrocarbons can be measured. In one
embodiment, there are some overlapping species such as methane,
ethane and ethylene. In one embodiment, at OCV, the outlet gas
contains largely methane (greater than about 80%) with less than
about 1% of ethane and ethylene. This demonstrates the formation of
a hydrocarbon from an oxygenated species.
[0069] In one embodiment, the use of only nickel for the cathode
produces a large amount of methane. In one embodiment, a cobalt
composite cathode may be used to form propane. In some embodiments,
other catalytic materials may be used for the cathode. In one
embodiment, cobalt, molybdenum and rhenium are deposited on the
surface of the cathode to enable in-situ electro-deoxygenation and
to prevent cracking of hydrocarbon which may produce coke. In one
embodiment, the product distribution depends on one or more of the
following: operating temperature, initial concentration of bio-mass
material, applied voltage, electric current, and the composition of
cathode.
[0070] In one embodiment, the feed rate of bio-mass vapors into the
electrochemical cell is approximately 1.67 g/hr (approximately
2.24.times.10.sup.-4 mole/min). In another embodiment, guaiacol is
fed into an electrochemical cell at approximately 1.67 g/hr. In one
embodiment, the feed rate for H.sub.2 is approximately 10 sccm
(approximately 4.46.times.10.sup.-4 mole/min or approximately
0.013452554 moles/hr). In another embodiment, the feed rate of
steam is approximately 6.6 sccm (approximately
2.95.times.10.sup.-4). In one embodiment, the feed rate for N.sub.2
is approximately 30 sccm. In one embodiment, H.sub.2 is not fed
into an electrochemical cell, because it will be generated by steam
electrolysis. In one embodiment, oxygen is available from guaiacol
at a rate of approximately 2.24.times.10.sup.-4 mole/min. In one
embodiment, oxygen is available from steam at a rate of
approximately 1.48.times.10.sup.-4 mole/min.
[0071] In one embodiment, the temperature of the electrochemical
cell is in a range between approximately 500.degree. C. and
approximately 600.degree. C. Alternatively, the temperature of the
electrochemical cell may be approximately 550.degree. C. In another
embodiment, the temperature of the electrochemical cell is
approximately 500.degree. C. In one embodiment, the temperature of
the electrochemical cell is approximately 600.degree. C.
[0072] FIG. 5 provides a conceptual process design for
approximately 20 gallons per day of hydrocarbon production facility
that would be hydrogen independent. Upon scale-up, such an
integrated plant would lead to economical production of
hydrocarbons. According to the embodiment of FIG. 5, bio-mass is
contained in bio-mass container 502. The bio-mass material may then
be transported from bio-mass container 502 to pyrolyzer 504, where
pyrolysis of the bio-mass may occur. Pyrolyzer 504 vaporizes the
bio-mass to produce bio-mass vapors. The bio-mass vapors may then
be passed through gas cleaner 508 to remove any contaminants before
being injected into EDOx unit 510. EDOx unit 510 is optimized to
operate at the exit temperature of pyrolyzer 504 such that gas
equilibrium is maintained, thereby minimizing the driving force for
coking.
[0073] In one embodiment, EDOx unit 510 can be a stack of planar
cells. In one embodiment, the stack of planar cells includes an
anode layer, an electrolyte layer, and a cathode layer. In one
embodiment, each planar cell is separated by an interconnect
material made of metal or ceramic or combinations thereof. In one
embodiment, the interconnect material is coated with an appropriate
material to prevent promotion of coking of the bio-oil vapors. In
one embodiment, EDOx unit 510 can be built using tubular cells or
other shapes to improve physical and process integration with the
pyrolyzer.
[0074] In one embodiment, oxygen gas is released from EDOx unit 510
and collected into oxygen vessel 512. Following pyrolysis in
pyrolyzer 504, the remaining char may provide cogeneration for
utilities at cogeneration site 506. The ash may be removed prior to
providing cogeneration for utilities. Hydrocarbon vapors are
released from EDOx unit 510. At this point, the hydrocarbon vapors
contain fewer oxygen atoms than prior to entering EDOx unit 510,
according to some embodiments. The hydrocarbon vapors are collected
from the EDOx unit 510 and passed through condenser 514 to condense
the hydrocarbon vapors into a mixture of hydrocarbon gases and
liquids. The mixture of hydrocarbon gases and liquids may then pass
through gas/liquid separator 516. The hydrocarbon liquids may then
be collected in vessel 518. In one embodiment, the hydrocarbon
gases that exit gas/liquid separator 516 may be used to provide
heat to pyrolyzer 504. In another embodiment, the hydrocarbon gases
may provide cogeneration for utilities at cogeneration site
506.
[0075] Besides containing oxygenated compounds, bio-mass oil
contains a combination of water soluble, organic soluble compounds.
When cooled, they phase separate and also become unstable, i.e.,
they polymerize and become difficult to process to make useful
fuels. In one embodiment, the process converts water-soluble
oxygenates into water insoluble hydrocarbons. In one embodiment,
the process allows direct transfer of pyrolysis vapors (from
pyrolyzer 504) to EDOx unit 510 without cooling the vapors. In one
embodiment, EDOx unit 510 operates efficiently over a range of
temperature between about 600.degree. C. to about 1000.degree. C.
In one embodiment, EDOx unit 510 operates efficiently over a range
of temperature between about 500.degree. C. to about 800.degree. C.
In one embodiment, EDOx unit 510 operates at a temperature as low
as about 400.degree. C. with the use of lower temperature
electrolyte system.
[0076] In one embodiment, the pyrolysis vapor can also be slightly
heated from the typical pyrolyzer temperature of about 500.degree.
C. to match the operating temperature of EDOx unit 510. In another
embodiment, the pyrolysis vapor can also be slightly heated from
the typical pyrolyzer temperature of about 550.degree. C. to match
the operating temperature of EDOx unit 510. In one embodiment, the
pyrolysis vapor can also be slightly heated from the typical
pyrolyzer temperature of about 600.degree. C. to match the
operating temperature of EDOx unit 510.
[0077] According to the embodiments, more than about 95% carbon and
hydrogen efficiency is attainable in the proposed process. This is
possible because oxygen is removed in its elemental form, and not
as a molecule combined with carbon or hydrogen. In some
embodiments, energy is required to produce 02 (g), and this energy
is supplied by electricity, which is stored in an energy dense
liquid hydrocarbon fuel where the hydrogen and carbon come from
cellulosic bio-mass. In one embodiment, this process is based on
high temperature electrolysis process. The high temperature
electrolysis process is endothermic, while the resistive loss (i.e.
electrical resistance of the membrane and electrodes) is
exothermic. An approximately 100% efficiency of electricity to
heating value of product may be achieved by carefully selecting the
process operating voltage so that the endotherm and exotherm match.
The voltage, commonly termed thermal neutral voltage V.sub.tn is
calculated as: V.sub.tn=(.DELTA.H)/(nF), where .DELTA.H is the
enthalpy of reaction, n is the number of electrons involved, and F
is Faraday's constant.
[0078] In one embodiment, the process has a demonstrated efficiency
of greater than about 96% for both steam electrolysis to make
hydrogen, and CO.sub.2 and steam co-electrolysis to make syngas in
an about 4 kW laboratory module. In one embodiment, the .DELTA.H
value depends on the relative amounts of various molecules. In one
embodiment, the overall electrical efficiency is expected to be
about 90% or greater. In one embodiment, the net positive impact on
efficiency is a range between about 16% and about 28% per unit of
upgraded hydrocarbons.
[0079] The life cycle GHC intensity of the process saves about 20%
of the energy required to upgrade pyrolysis oil relative to the
process of hydrotreating. In one embodiment, the process leads to a
GHG intensity in a range of approximately 28 CO.sub.2e/MJ to
approximately 30 CO.sub.2e/MJ of hydrocarbon produced, relative to
approximately 39 CO.sub.2e/MJ of hydrotreating as estimated using
the GREET model and literature data. Thus, according to some
embodiments, the process results in a GHG intensity reduction in a
range of approximately 25% to approximately 30%. In embodiments
where renewable electricity is used for conversion of the bio-mass
material, the process may result in a GHG intensity reduction in a
range of approximately 60% to approximately 70%.
EXAMPLES
[0080] Other uses, embodiments and advantages of the systems and
methods for upgrading bio-mass material in an electrolytic cell are
further illustrated by the following examples, but the particular
materials and amounts cited in these examples, as well as other
conditions and details, should not be construed to unduly limit the
systems and methods for upgrading bio-mass material in an
electrolytic cell.
Example 1
[0081] In one example, the electrochemical cell was an
(yttria-stabilized zirconia) YSZ electrolyte based cell. The
cathode was nickel-ceria cermet and the anode was lanthanum
ferrite-cobaltite type perovskite. It was tested at about
700.degree. C. using acetic acid with N.sub.2 as the carrier gas
and steam with N.sub.2 as the carrier gas. The two streams were fed
from separate heated containers and the resulting vapors were mixed
prior to entry into the fuel manifold of the cell. This was tested
at three different current densities as well as at the open circuit
condition (OCV). Hydrogen was added to the steam in the OCV
condition to prevent oxidation of the fuel electrode. The exhaust
product gas was analyzed using a micro-GC for each condition. This
cell was also tested on acetone with N.sub.2 as the carrier gas and
with steam and N.sub.2 at both approximately 700.degree. C. and
approximately 800.degree. C. test temperatures. Three different
current densities were tested at each temperature and GC samples
were analyzed for each. The gas composition results from the GC
sampling for each test condition are given below in Table 2.
TABLE-US-00002 TABLE 2 Product gas analysis from electrochemical
cell on acetic acid and acetone. Temp Organic Voltage Current H2
CH4 CO CO2 Ethene Ethane Propane Butane 700 Acetic Acid 1.300 0.113
39.4% 1.8% 34.0% 5.9% 18.3% 700 Acetic Acid 1.115 0.082 36.9% 1.4%
39.1% 5.7% 16.2% 700 Acetic Acid 0.973 0.050 35.5% 1.5% 40.1% 5.8%
16.4% 700 Acetic Acid 0.828 0.000 65.9% 1.2% 22.2% 2.9% 7.6% 700
Acetone 1.300 0.046 79.5% 3.0% 7.1% 0.4% 0.2% 0.2% 0.7% 9.0% 700
Acetone 1.450 0.080 70.6% 9.0% 6.0% 0.8% 0.2% 0.2% 0.7% 12.4% 700
Acetone 1.600 0.116 70.1% 9.1% 6.1% 0.8% 0.2% 0.2% 0.8% 12.8% 800
Acetone 1.300 0.175 48.4% 27.4% 19.3% 0.9% 0.6% 0.6% 0.9% 0.7% 800
Acetone 1.450 0.244 46.5% 28.8% 19.7% 0.6% 0.7% 0.7% 0.8% 0.8% 800
Acetone 1.600 0.331 43.1% 30.9% 20.9% 0.7% 1.0% 1.0% 1.0%
[0082] From Table 1, it can be seen that H.sub.2 production is high
from the electrolyzed steam and that it is more favored using
acetone over acetic acid. Also, using acetone at approximately
800.degree. C. produces more CH.sub.4 and CO with less butane than
is produced using acetone at approximately 700.degree. C.
Example 2
[0083] In order to reduce the cell's operational temperature to one
that is more in line with the bio-oil reactor, lower temperature
cells made from doped ceria electrolyte were tested. In this
example, the cathode was nickel-ceria cermet and the anode was Sr
doped lanthanum cobaltite. The electrochemical cell was tested at
approximately 600.degree. C., approximately 550.degree. C., and
approximately 800.degree. C. using acetone with N.sub.2 as the
carrier gas and steam with N.sub.2 gas. Hydrogen gas was only
flowing with the steam during OCV condition to prevent oxidation of
the electrode. This cell was also operated on furfural at
approximately 550.degree. C. with N.sub.2 as carrier gas and steam
with N.sub.2 as the carrier gas. Several current densities were
evaluated for each of the temperature and organic combinations and
a list of their product compositions is below in Table 3.
TABLE-US-00003 TABLE 3 Product gas analysis from electrochemical
cell on acetone and furfural. Temp Organic Voltage Current H2 CH4
CO CO2 Ethene Ethane Propane Butane Pentane 600 Acetone 1.15 0.25
92.8% 0.5% 2.6% 1.8% 2.2% 600 Acetone 1.30 0.50 95.0% 0.5% 2.4%
0.6% 1.6% 600 Acetone 1.45 0.86 93.7% 0.5% 2.7% 1.1% 2.0% 550
Acetone 1.15 0.13 91.6% 1.0% 2.8% 2.0% 2.6% 550 Acetone 0.87 0.00
89.9% 1.7% 4.9% 1.6% 1.8% 550 Acetone 1.15 0.12 92.1% 1.2% 2.8%
2.1% 1.9% 550 Acetone 1.30 0.34 92.2% 1.1% 2.4% 2.4% 2.0% 550
Acetone 1.45 0.45 93.4% 1.0% 1.6% 2.0% 2.1% 800 Acetone 0.69 0.00
51.3% 22.2% 23.6% 1.8% 1.0% 0.7% 1.5% 800 Acetone 1.00 0.16 50.0%
23.2% 20.2% 3.2% 1.1% 0.8% 1.4% 800 Acetone 1.30 0.40 49.5% 23.7%
20.3% 3.2% 1.1% 0.8% 1.4% 800 Acetone 1.60 0.81 48.9% 24.4% 20.2%
3.0% 1.1% 0.8% 1.5% 550 Furfural 0.65 0.00 43.1% 12.7% 25.6% 15.0%
3.5% 550 Furfural 1.30 0.21 28.3% 22.1% 31.2% 15.0% 3.4% 550
Furfural 1.60 0.26 29.5% 19.1% 34.3% 12.6% 4.5%
[0084] While operation on acetone at approximately 600.degree. C.
and approximately 550.degree. C., the H.sub.2 production was quite
high as compared to operation at approximately 800.degree. C. I can
be seen in Table 3 that on acetone at approximately 550 or
approximately 600.degree. C. there was no ethene or ethane
produced, while at approximately 800 C there was a small quantity
of each made. The methane and carbon monoxide production were also
higher at approximately 800.degree. C. The product mixture may
change with change in specific composition of the cathode
material.
[0085] When the cell was operated on furfural at approximately
550.degree. C., there was no methane in the product gas stem and
the CO.sub.2 and ethane were much higher than the acetone runs.
There was also no propane made, but pentane was made instead.
Example 3
[0086] Another ceria electrolyte cell was tested on furfural at
550.degree. C. using two different current density values and at
OCV. The furfural was vaporized at the temperature of approximately
50.degree. C. with N.sub.2 flowing and the steam had only N.sub.2
as the carrier gas except for the OCV condition, which also had
additional H.sub.2. Table 4 below contains the GC results for the
gas product at different current density and at OCV.
TABLE-US-00004 TABLE 4 Product analysis from electrochemical cell
on furfural. Temp Organic Voltage Current H2 CH4 CO CO2 Ethene
Ethane Acetylene Propane Butane Pentane 550 Furfural 1.30 0.06 3.0%
20.1% 35.3% 0.8% 1.2% 36.6% 3.1% 550 Furfural 1.60 0.10 1.8% 18.1%
34.5% 1.0% 1.0% 40.9% 2.8% 550 Furfural 0.76 0.00 96.7% 0.3% 0.1%
2.9%
[0087] The current densities for the same voltages were lower than
those for the electrochemical cell of Example 2. Something to note
is that in the electrochemical cell of Example 3, there was no
ethane formed like in the electrochemical cell of Example 2, but a
little acetylene and ethane and quite a bit of propane were
formed.
Example 4
[0088] In one example, the electrochemical cell was another ceria
electrolyte cell that was tested at approximately 550.degree. C.
using several different organics. It was independently tested on
guaiacol, furfural, phenol, and syringol. The cell was tested at
different current densities for each material except for furfural
and syringol where it was tested at one condition to generate some
condensate for Gas Chromatograph/Mass Spectrometer (GCMS) testing.
All other materials were also left on test at one current density
long enough to generate some condensate to evaluate using the GCMS.
Nitrogen was used as the carrier gas for each chemical and N.sub.2
and H.sub.2 was used as a carrier gas for the steam, but at a
reduced flow rate. The water temperature was lowered to
approximately 50.degree. C. from the temperature of approximately
82.degree. C. used in previous cells to reduce the amount of
available water to electrolyze. Table 5 contains the gas phase GC
results for each condition.
TABLE-US-00005 TABLE 5 Output gas compositions using model
compounds Temp Organic Voltage Current H2 CH4 CO CO2 Ethene Ethane
Propane Butane Pentane 550 Guaiacol 1.3 0.24 85.3% 2.7% 5.4% 1.9%
0.3% 0.1% 4.0% 0.2% 0.1% 550 Guaiacol 1.39 0.36 85.1% 2.9% 5.4%
1.8% 0.3% 0.2% 3.9% 0.3% 0.1% 550 Guaiacol 0.845 0 80.2% 3.7% 7.3%
3.8% 0.3% 0.2% 3.9% 0.4% 0.1% 550 Guaiacol 1.55 0.748 83.0% 3.3%
6.3% 1.8% 0.3% 0.2% 4.6% 0.3% 0.1% 550 Furfural 1.38 0.36 89.9%
3.7% 2.2% 0.1% 3.9% 0.2% 550 Furfural 1.35 0.341 91.3% 2.4% 2.3%
0.1% 2.5% 1.4% 550 Phenol 1.35 0.43 96.8% 0.9% 0.5% 1.9% 550 Phenol
0.742 0 85.7% 1.6% 5.6% 7.1% 550 Phenol 1.4 0.351 88.3% 1.7% 4.8%
5.2% 550 Phenol 1.15 0.092 88.0% 1.7% 5.0% 5.3% 550 Phenol 1.6
0.757 86.4% 1.6% 5.5% 6.4% 550 Syringol 1.63 0.33 73.3% 1.7% 3.9%
12.3% 0.4% 8.3% 0.2% 550 Syringol 1.69 0.142 71.3% 2.1% 5.0% 12.2%
0.3% 0.1% 8.7% 0.2%
[0089] These materials all produced CO, CO.sub.2 and propane in the
gas phase products. The guaiacol and syringol were similar and also
produced methane, ethene, ethane, and butane. The guaiacol did
produce some pentane. The phenol only produced the CO, CO.sub.2,
and propane, while the furfural also produced ethane and
pentane.
[0090] The liquid condensate from furfural, guaiacol and syringol
tests included one or more of partially or fully deoxygenated
liquid hydrocarbons such as: toluene, 2-cyclopenten-1-one,
furfural, 2-5-dimethylfuran, methyl isobutyl ketone, p-xylene,
4,4-dimethyl-2-cyclopenten-1-one, styrene, anisole, benzaldehyde,
phenol, benzofuran, salicylaldehyde, o-cresol, p-cresol, m-cresol,
2-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2-ethylphenol,
2-ethyl-6-methylphenol, naphthalene, 3-methoxyanisole,
bicyclo[4,2,0]octa-1,3,5-triene, cyclopentanone,
2-methyl-2-cyclopenten-1-one, indene, 2,6-xylenol, 2,3-xylenol,
2,5-xylenol, dihydronaphthalene, guaiacol,
3-methyl-2-cyclopenten-1-one, catechol, 1-methylcatechol,
4-methylcatechol, 3-methylpyrocatechol, syringol, 3-methylcatechol,
1H-indenol, 1-indanone, dibenzofuran, 2-methylbenzofuran, phenyl
methyl acetylene, 3-butenoic acid, 1-(2-furanyl) ethenone,
2,2-bifuran, 5-methylfurfural, benzeneacetaldehyde,
2H-pyran-2-one.
[0091] Although the invention herein has been described in
connection with described embodiments thereof, it will be
appreciated by those skilled in the art that additions,
modifications; substitutions, and deletions not specifically
described may be made without departing from the spirit and scope
of the invention as defined in the appended claims. It is therefore
intended that the foregoing detailed description be regarded as
illustrative rather than limiting, and that it be understood that
it is the following claims, including all equivalents, that are
intended to define the spirit and scope of this invention.
* * * * *