US 20100175320Al

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2010/0175320 A1
(43) Pub. Date:

Schuetzle et al.
(54)

ENERGY EFFICIENT SYSTEM AND

PROCESS FOR THE CONTINUOUS

Publication Classi?cation
(51)

Int Cl

PRODUCTION OF FUELS AND ENERGY

'

FROM SYNGAS

Dennis Schuetzle, Grass Valley, CA

(US); Ronald G. Hurley, Sarasota,
FL (US); Robert W. Schuetzle,
Sacramento, CA (U S)

(2006.01)

US. Cl. ............................................. .. 48/76; 48/203

57
( )

ABSTRACT

A system and apparatus is provided that maximizes mass and

COrreSpOndenCe AddreSSI

energy conversion ef?ciencies in an integrated thermochemi

cal process for the conversion of fossil fuel or renewable

McKinney Law Group, APC

851 MOraga R0311, BllIlgal0W B

biomass to synthesis gas. The system combines gasi?cation,

catalytic conversion of gas to liquid, electricity generation,

Lafayette, CA 94549 (Us)

steam and chilled Water generation With a system controller to

(73)

'

C10J 3/00
(52)

(75) Inventors:

Jul. 15, 2010

maximize the conversion ef?ciency from syngas to merchant

Asslgnee?

PACIFIC RENEWABLE FUELS

LLC, Sacramento, CA (Us)

able products over the ef?ciency of syngas alone burned as a

fuel. A clean synthesis gas stream is introduced into a cata

11/966,788

generate liquid fuel from C0 and H2 While concentrating CH4

Dec 28 2007

product stream. The methane rich stream is introduced into an

lytic reactor that utilizes specially formulated catalysts to

(21) Appl' NO:

_

and other combustible, but non-reactive gases in the syngas

(22)

Flled'

(60)

Related U's' Apphcatlon Data

Provisional application No, 60/882,755, ?led on Dec,
29, 2006.

10

engine for the production of electricity and heat While the

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unreacted CO and H2 can be recycled to produce additional

liquid fuel. Excess heat can be used for other co-located
processes and facilities.

26

Hydrogen

Generator

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(Computer)

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Patent Application Publication

Jul. 15, 2010 Sheet 1 0f 2

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US 2010/0175320 A1

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US 2010/0175320 A1

ENERGY EFFICIENT SYSTEM AND

PROCESS FOR THE CONTINUOUS
PRODUCTION OF FUELS AND ENERGY
FROM SYNGAS
CROSS-REFERENCE TO RELATED
APPLICATIONS

[0001] This application claims priority from US. provi

sional application Ser. No. 60/882,755 ?led on Dec. 29, 2006,

incorporated herein by reference in its entirety.

Jul. 15,2010

signi?cantly expanded With the economical conversion of

biomass and fossil resources to synthesis gas With further
conversion to liquid fuels. Rather than burning biomass or
fossil resources directly, gasi?cation, a thermo-chemical pro
cess is used to produce a mixture of carbon monoxide, hydro
gen and methane, knoWn as syngas. The resulting syngas is
more versatile than the original solid biomass or fossil
resources and has energy conversion possibilities that have

advantages over other outputs created by direct burning.

[0011] Since the early 1900s, a number of thermochemical
processes have been developed for the conversion of carbon

STATEMENT REGARDING FEDERALLY

SPONSORED RESEARCH OR DEVELOPMENT

[0002] Not Applicable

INCORPORATION-BY-REFERENCE OF
MATERIAL SUBMITTED ON A COMPACT DISC

[0003] Not Applicable

aceous materials derived from reneWable and fossil

resources. These thermochemical processes convert carbon

containing compounds into syngas, a mixture comprised pri

marily ofCO and H2, Which can also contain amounts of CO2

and CH4 With traces of other hydrocarbons. The technology

for the production of biomass and fossil resources continues

to be developed and advancements in production ef?ciency

have been seen. Improved conversion technologies can pro

vide bene?ts ranging from reduced environmental impacts to

BACKGROUND OF THE INVENTION

[0004] 1. Field of the Invention

[0005] This invention pertains generally to an improved
energy ef?cient process for the continuous, co-production of
liquid fuels, electricity and heat from syngas, and more par
ticularly to a system and method Which integrates thermo

chemical syngas production, catalytic conversion processes

and electricity and heat production systems in a manner that

maximizes the thermal energy ef?ciency for the conversion of

carbonaceous materials to electricity and liquid fuels.
[0006] 2. Description of RelatedArt
[0007] The WorldWide demand for energy and transporta
tion fuels is groWing rapidly as fossil energy sources become

more depleted, expensive, and environmentally problematic.

A signi?cant percentage of the production of electricity in the
United States comes from conventional pulveriZed-fuel-?red
boilers linked to a conventional steam cycle. Such generation
systems have modest ef?ciencies and contribute to the global

emissions of nitrogen oxides, sulfur oxide, carbon dioxide,

and particulate matter. Furthermore, in some coal combustion
plants, only a third of the energy value of the coal is actually
converted into electricity and the rest is lost as Waste heat.
[0008] Improved and innovative systems are needed that
Will provide alternative energy sources and options to meet

future energy needs and address rising pollution issues. Even

though there are many technologies that are capable of chang
ing energy fuels from one form to another, existing energy
conversion systems have limited ef?ciencies and notable
Waste.

[0009]

This has also driven the development of neW energy

technologies that are capable of converting non-petroleum

higher energy ef?ciency as Well as secure and reliable elec

trical poWer production and fuel availability.

[0012] Also discovered in the early 1900s Was the process
for hydrogenation of CO over transition metal catalysts to

produce liquid hydrocarbons and oxygenated compounds.

Numerous catalyst formulations have been developed to pro
duce liquid fuels and chemicals from syngas feedstock. For
example, Fe, Co and Ni based catalysts have been used exten

sively for the synthesis of mixtures of paraf?ns and ole?ns

that can be converted to gasoline and diesel fuels. Copper
based catalysts have been used for methanol and mixed alco

hol production. Other metals have been proposed for deriving

other speci?c products, for example Rh based catalysts devel
oped for acetic acid, acetaldehyde and ethanol production.
Also mixtures of catalyst metals (e. g. Rhodium and Copper)
have been shoWn to give higher selectivity for the production
of ethanol. These catalysts typically operate at elevated pres
sures (500-2000 psig) and temperatures (400-6500 F.). The
conversion ef?ciencies of the primary reactants (CO and H2)
to fuels can be loW for alcohol synthesis (15-30%) and higher

for the synthesis of chain hydrocarbons (40-80%). The

amount of gas conversion decreases With gas hourly space

velocity but yield and selectivity for certain products can be

improved With higher space velocity. For these synthesis cata
lysts, optimum space velocities are on the order of 1000 to

10,000 hrl using normaliZed gas volumes.

The chemistry involved in synthesis can include the

[0013]

folloWing generalized reactions.

CO+3H2>CH4+H2O

nCO+(2n+l )H2 >CnH2n+2+nH2O

(Methanation)

(Alkanes/Paraf?ns)

and non-fossil fuel resources into useable fuels and electric

ity. Part of this challenge is to develop loW cost and scalable

systems that can achieve high energy conversion ef?ciencies.
[0010] It has long been knoWn that carbonaceous materials
such as agricultural, forest and municipal Waste (biomass)
as Well as natural gas, coal, oil shale and oil sands (fossil
resources) can be converted into combustible gases by ther

mochemical processing. These thermochemical processes

utiliZe conversion technologies such as gasi?cation, reform
ing, pyrolysis, catalysis and other relevant processes for the

nCO+2nH2>C,,H2,,+nH2O

nCO+2nH2>C,,H2n+1OH+(n1)H2O

(Alkenes/Ole?ns)

(Alkanols/Alcohols)
(Water-Gas Shift)

[0014] In the synthesis of hydrocarbon and alcohol com

pounds With tWo carbons or greater, 100% selectivity for the
desired compounds is not currently achievable. In addition to
a mixture of liquid products, some gaseous side products are

conversion of fossil fuels (natural gas, coal, oil, oil shale, etc)

generated including carbon dioxide from the Water-gas shift

and reneWable biomass to synthesis gas (syngas). For

example, the energy options available to the World could be

reaction and methane from the above methanation reaction.

As described in previous systems, methane canbe recycled by

US 2010/0175320 A1

being reformed back to CO and H2. Steam reforming has been

described for the production of additional CO and H2. The CO
and H2 are then added to the syngas at a point before the

catalytic reactor. Since these reformers require elevated pres

sures and temperatures, additional external energy is needed,

resulting in loWer thermal energy ef?ciency for the produc

tion processes.

Jul. 15,2010

prised primarily of CO, H2, CO2 and CH4, is derived from any
carbonaceous feedstock material such as agricultural, forest
and municipal Waste as Well as natural gas, coal, oil shale and

oil sands by utilizing conversion technologies such as gasi?

cation, reforming, pyrolysis, catalysis and other relevant pro
cesses.

[0015] Accordingly, there is a need to identify and develop

advanced technologies that Will improve the ef?ciency or
reduce the cost of producing electricity, liquid fuel, fuel

[0020] The syngas is pressurized and fed to a synthesis

reactor to be converted to desired liquid products. Catalyst

gases, chemicals and heat recovery utilities like steam Within

an integrated system. There is also a need for a system With

such as alcohols and liquid hydrocarbons. The liquidproducts

are cooled and separated from the un-reacted gases. Catalyst

the capability of producing electricity, fuel gases, steam, liq

formulations are also selected to convert CO and H2 in the

syngas to the desired fuel products such as alcohol and liquid

uid fuels and chemicals, or various combinations of these

materials, While greatly reducing air pollutants and green

house gas emissions. The present invention meets these needs
as Well as others and is a substantial improvement over the art.

BRIEF SUMMARY OF THE INVENTION

[0016]

The present invention is an integrated system With

processes con?gured to generate liquid fuels, electricity and

heat from carbonaceous fuel sources. The preferred system
combines and maximizes the carbon and energy conversion
potential and ef?ciency of the associated components or sub
systems to produce a system for the co-production of fuels
and electricity from syngas. The process can produce liquid
fuels and electricity from carbonaceous feedstock at net ther
mal energy ef?ciencies of greater than 40-50%, Which are

signi?cantly higher than fuel synthesis or electricity genera

tion alone.

[0017] Some of the other advantages of the present inven

tion over the prior art include simpli?ed process steps through
the real-time monitoring of gas composition before and after
the catalyst reactor, monitoring of process conditions (such as
temperature, pressure and gas ?oW velocity) optimization of

hydrogen/carbon monoxide gas composition using a hydro

gen generator, the use of neural netWork algorithms and

kinetic/thermodynamic models With feed-back control, for

process optimization, and the use of chemical species (eg
methane) that are relatively catalytically non-reactive to gen
erate electricity and heat. This simpli?ed system optimizes

fuel, electricity and heat production, resulting in high net

energy ef?ciencies and system ?exibility.
[0018] The main subsystems include: syngas generation, a
catalytic reactor for the production of liquid fuels from syn
gas, a hydrogen generator, on-line analytical instruments for
monitoring gas phase species before and after the catalyst,
on-line sensors for monitoring temperature, pressure and gas
How, a process control system that collects on-line data and
controls catalyst process conditions, a gas/liquid separator, a

gas-recycle system and equipment for the production of elec

tricity and heat from the gas-phase components that Were not
used for conversion to fuels. These subsystems can be

adapted to produce different types of liquid fuels, electricity

and heat that can be sold as commercial products.
[0019] In one embodiment of the invention, syngas and

hydrogen generators are provided. In another embodiment,

the syngas and hydrogen are provided from a source outside

of the system. Carbon monoxide may also be supplemented in

one embodiment. The system is ideally suited for small and
medium sized, distributed conversion facilities that are

formulations are selected to convert CO and H2 to products

hydrocarbon fuels Without signi?cantly altering the more

energy rich chemical species such as methane and other cata

lytically, non-reactive species in the syngas.

[0021] A portion of these un-reacted gases can be recycled
to the synthesis reactor While the remainder is used to gener
ate electricity and steam. The process of catalysis and recy

cling concentrates species of combustible but catalytically

non-reactive species (like CH4) in the product gas.
[0022]

The desired liquid products are separated from the

energy enriched gas stream and an on-line process analyzer is

used to monitor the concentrations of the primary gas species.

This information, along With process control algorithms, is

used to adjust the amount of gas that is recycled through the
catalyst versus the amount of gas that is sent to the engine/

generator or gas-turbine. This integrated, continuous process

results in an optimized production of liquid fuels, electricity

and heat.

[0023] A portion of the product gas and the electricity gen

erated by the system may be used to provide process energy
for various parts of the system including the syngas generator,
a hydrogen generator and other equipment described in detail
beloW. An analog and/ or digital control system optimizes the

gas composition for production of fuels and electricity.

[0024] Some of the electricity and heat may be used to
produce hydrogen, Which may be added to the incoming
syngas to increase the yield of liquid fuel products. The com
position of the syngas stream may be further supplemented by
passing carbon dioxide gas over heated charcoal to form
carbon monoxide increasing the concentration of this gas to
the reactor. Hydrogen gas may also be added to bring the
concentrations of CO and H2 to the desired ratio.

[0025]

The electricity and heat generated in this system

may also be used to run the process and it may also be used as
a clean energy source for the syngas production systems.

Excess electricity may be distributed to the regional electrical

grid. The excess heat can be used for other co-located pro
cesses and facilities.

[0026]

According to one aspect of the invention, a system

for the production of liquid fuels and electricity from syngas

is provided that l) generates synthesis gas (syngas) from a
carbonaceous feedstock (e.g. agricultural, forest and munici
pal Waste, natural gas, coal, oil shale and oil sands) using a

but may also be used in larger designs that may function as

thermochemical process, catalytic reformer and/or other rel

evant technology or combination thereof; 2) introduces a

regional fuel and electricity production centers. Syngas, com

clean syngas stream (primarily CO, H2, CH4, CO2 and H20 at

located near feedstock resources for the production of syngas

US 2010/0175320 A1

varying concentrations) to a catalytic synthesis reaction sys

tem to simultaneously generate liquid fuel from CO and H2
While concentrating CH4 and other combustible but non-re
active gases in a gas product stream; and 3) introduces the
CH4 rich product gas stream into an engine, gas-turbine or
other relevant technologies for the production of electricity
and heat.
[0027] According to another aspect of the invention a sys

Jul. 15,2010

BRIEF DESCRIPTION OF THE SEVERAL

VIEWS OF THE DRAWING(S)

[0035]

The invention Will be more fully understood by ref

erence to the folloWing draWings Which are for illustrative

purposes only:
[0036]

FIG. 1 is a system How diagram of a process accord

ing to the present invention.

[0037] FIG. 2 is a system How diagram of an integrated

tem is provided Where catalyst formulations in the synthesis

system of syngas production, liquid product production and

reactor are selected to operate under conditions in Which CO

steam and electrical production according to the invention.

reacts e?iciently With H2 to produce alcohol, diesel, gasoline,

ether or hydrogen fuels as Well as create conditions in Which

CH4 and other light hydrocarbons are relatively non-reactive

over the catalysts.

[0028] Process optimiZation is optionally facilitated by the

injection of additional hydrogen into the catalyst reactor pro
duced by electrolysis or other source to improve liquid fuel
production ef?ciency. The process control computer is used
to change the proportion of liquid fuel production to electric

ity/heat production and dictated by real-time electricity and

liquid-fuel market ?uctuations and requirements.
[0029] According to another aspect of the invention, a sys
tem is provided that monitors the composition of the pre- and
post-catalyst gas stream and uses that information With an

on-line process controller to optimiZe the recycle ratio of the

post-catalyst gas stream and other process controls With the
purpose of generating a CO and H2 rich gas stream suitable
for fuel synthesis via catalysis, as Well as a CH4 and other
light combustible rich gas stream that is ideal for the produc

DETAILED DESCRIPTION OF THE INVENTION

[0038]

The present invention is an integrated, continuous

process that maximizes the carbon and energy conversion

ef?ciencies for the simultaneous production of liquid fuels,

electricity, and heat from syngas. The process is optimiZed
using an on-line computer system With the use of continuous
gas analyZers and process algorithms to control and to maxi

miZe product yields and energy ef?ciency. This process

invention signi?cantly reduces the complexity of current,
commercial systems for the synthesis of liquid products,
resulting in signi?cantly loWer capital and production costs.
[0039]

As seen schematically in FIG. 1 and FIG. 2, the

system for producing liquidmaterials and combustible gas for

the generation of electricity and heat has several subsystems
of processes. The primary processes are syngas generation,

hydrogen generation, synthesis, liquid separation, gas recy

cling, electricity generation, heat recovery and system con
trol.

[0040] The syngas production and liquid material produc

tion of electricity and heat.

[0030] Another aspect of the invention provides a control
ler Wherein chemical thermodynamic and energy models and/
or advanced learning algorithms (e.g. neural networks) are
used in an on-line digital and/or analog process control sys
tem to help determine the desired process conditions and split
ratios of the gas stream to the catalysts and the engine/gen

tion subsystems 12 of the production system 10 of FIG. 2 are

shoWn in FIG. 1. The liquid production subsystem 12 can
produce different liquid materials from a source of syngas
depending on the selection of the reactor catalysts and reac
tion conditions.
[0041] Synthesis gas is de?ned as a gas comprising prima

erators and/ or gas turbine/ generators.

source. Typical synthesis gas includes carbon monoxide,

hydrogen and lesser amounts of carbon dioxide (CO2) and

[0031] According to another aspect of the invention the

energy ef?ciency of the process is maximized by monitoring
the pre- and post catalyst gas stream composition and using
that information in an on-line process control system to vary

fuel production vs. electricity and heat production. The on

line process control system preferably employs kinetic/ther

modynamic models and neural netWork systems.
[0032]

According to a further aspect of the invention, sen

sors monitor the gas composition at one or more locations, in

combination With chemical thermodynamic and energy mod

els to control the addition of the hydrogen into the pre-catalyst
syngas stream to enhance the catalyst conversion ef?ciencies
of CO, CO2 and other catalytically reactive species to fuels.
[0033] Yet another aspect of the invention provides a pro
cess control system to change the proportion of fuel produc
tion to electricity and heat production, depending upon real
time market conditions. For example, When there is a peak
load demand for electricity, the amount of electricity can be
increased to help meet that demand.
[0034] Further aspects of the invention Will be brought out

in the folloWing portions of the speci?cation, Wherein the

detailed description is for the purpose of fully disclosing
preferred embodiments of the invention Without placing limi
tations thereon.

rily carbon monoxide (CO) and Hydrogen (H2) from any

other useful gases such as methane (CH4) as Well as small

amounts of light para?ins, such as ethane and propane. It may

also contain gases such as nitrogen, argon, oxygen-contain
ing compounds and Water in a gaseous state. HoWever, the
preferred ratio of hydrogen to carbon monoxide is 0.5 to 5,

and 0.75 to 2.5 by molar ratio is particularly preferred.

Accordingly, the proportion of carbon monoxide and hydro
gen together in the reactant gas is preferably about 20% to
about 100% by volume.

[0042] The syngas production subsystem 14 preferably has

a syngas generator 16 that processes fuel 18 to produce a

stream 20 of synthesis gas. Although a syngas production

subsystem 14 is provided in the embodiment of FIG. 1 and
FIG. 2, it Will be understood that syngas may be transported
by pipeline from a storage source or production source out

side of the system.

[0043] Syngas can be generated from a Wide variety of
carbonaceous fuel sources 18 including petroleum Waste

products, coal, Wood, straW, Waste tires, natural gas, land?ll

gas, or any other carbon containing matter. Many technolo
gies have been developed to thermally convert a carbon
aceous feedstock to syngas. The speci?c method for produc
ing syngas and type of syngas generator are not essential to
the system 10. HoWever, the type of syngas generator 16 that

US 2010/0175320 A1

is selected is preferably one that has loW energy requirements.

Because one of the objectives of the apparatus and system is

Jul. 15,2010

to synthesize liquid fuels from C0 and H2, technologies that

[0050] In one embodiment, the excess thermal energy is

converted to electrical energy for use in other parts of the
system or for sale on the poWer grid. For example, steam can

maximize the production of these gases are preferred.

be generated through a heat exchanger in the syngas out?oW

Examples of preferred technologies for this invention include

pyrolyzers, gasi?ers, steam or hydro-gasi?cation systems,

by either convection or conduction. The resulting steam can

be used to drive a turbine or other electrical generation device
as Well as used in other parts of the system or sold for other

steam reformers, autothermal reformers or combinations of

these technologies.
[0044] Currently, there are three types of gasi?ers: ?uidized
bed types, ?xed bed types and entrained ?oW types. In the
typical gasi?cation process, the fuel 18 is heated to a very
high temperature in the range of 10000 C. to 15000 C., While
under pressure (20 bars to 85 bars). Controlled amounts of
steam and oxygen are introduced to produce tWo sets of

reactions. The ?rst reaction is a partial oxidation of the fuel 18

that produces additional heat required for the second set of

reactions (pyrolysis) Which are endothermic. As a result, vir

tually all of the organic material is gasi?ed into primarily

carbon monoxide and hydrogen and the inorganic material is
converted to slag.

[0045] The technology used for syngas generation prefer

ably meets other criteria. The ratio of H2 to CO can be impor
tant for synthesis and a ratio of 0.5 to 5.0 is preferred, a ratio
of 0.75 to 2.5 is optimally preferred.
[0046] The amount of CO2 in the syngas can also impact the

synthesis activity, depending on the type of catalyst utilized.

Accordingly, a preferred maximum CO2 concentration in the
syngas ranging from 0-25% is preferred, 0-10% is optimally
preferred. Therefore, a system to remove some of the CO2
from the syngas stream may be included in the syngas gen
eration system 14 in one embodiment. In another embodi
ment, Waste heat is used to heat charcoal or other carbon
source and carbon dioxide gas is passed over the heated

charcoal to produce carbon monoxide, thereby increasing the

concentration of carbon monoxide and decreasing the con
centration of carbon dioxide Within the syngas stream.
[0047] Catalyst contaminants like sulfur and chlorine con

taining gases, tars, and particulates may also require removal.

Gas cleaning technologies like scrubbers, traps, precipitators,

etc. may be included in the syngas generation system in
certain embodiments.

[0048] Since syngas generation is generally an endother

mic process that requires heat to produce the reaction tem
peratures, heat from the fuel feedstock 18, the generated
syngas or from another external source is required to maintain
a continuous reaction. The source of the heat required for the

industrial uses of steam.

[0051] In order to maintain the proper balance of CO to H2

in the syngas for the desired synthesis reactions, the introduc
tion of hydrogen to the syngas may be bene?cial. An on-line
continuous gas analyzer 22 optionally monitors the concen
trations of carbon monoxide and hydrogen as Well as other
gases so that the composition of the feed gas 20 can be

manipulated to keep the proper ratio of CO to H2 approxi

mately constant by introducing additional hydrogen gas into
the gas stream. A stream of syngas With a generally consistent

composition can improve the conversion ef?ciency in the

reactors 28. Hydrogen generator 24 or other source of hydro
gen gas provides hydrogen gas to the stream of syngas 20 as

determined by the gas analyzer 22. The composition of the

gas can be sampled at different locations of the system and

analyzed by gas analyzer 22. For example, the composition of

gas entering 30 and exiting 36 the catalyst reactors 28 as Well
as the recycle gas 32 so that the gas composition can be

optimized and the production of liquid products can be maxi

mized.

[0052] In the preferred embodiment of the invention,

hydrogen can be generated from electrolysis of H20 and fed
into the feed syngas 30. High temperature electrolysis for the
production of hydrogen gas and oxygen gas takes advantage
of the Waste heat of the syngas generator or other heat sources

in the system. In another embodiment, hydrogen rich gas can

also be generated from natural gas by steam reforming or
from other emerging methods of production. Carbon monox
ide concentrations of the feed gas may optionally be supple
mented through carbon dioxide conversion or from an outside
source.

[0053] The system is controlled to provide the optimal ratio

of H2 to CO in the overall gas seen by the catalyst (including
feed syngas and recycle gas). A ratio of 0.5 to 5.0 is preferred;
a ratio of 0.75 to 2.5 is optimally preferred. This ratio may be

catalyst dependent.
[0054] The syngas stream 20 is compressed by a compres
sor 26 to approximately the desired reaction pressure that is in
the catalyst reactors 28. The combined feed syngas should be

pressurized before it enters the synthesis reactors 28. The

syngas generator 16 can come from any source. In one

reaction pressure impacts the productivity and selectivity of

embodiment, the reactor heat is supplied from the product gas

that remains after the liquid synthesis reactions to maximize
the e?iciency of the fuel synthesis. In other embodiments, this
heat can be supplied from the feedstock (auto-thermal), gen

the synthesis reactions in the reactors. Selection of the reac

erated syngas (before synthesis), or an external fuel source.

tion pressure is dependent on the type of catalyst, but gener

ally pressures in the range of 50-2000 pounds per square inch
(psi) may be required, and pressures of 50-1000 psi are opti
mally preferred. A suitable gas compressor 26 may include a

The thermal e?iciency of the syngas generation system

should be high to maximize system ef?ciency and reduce

phragm compressor, or other suitable device to achieve the

reciprocating compressor, centrifugal compressor, dia

parasitic load on the overall system. Thermal ef?ciencies of

greater than 50% are preferred and greater than 70% is opti

required reaction pressure. In the preferred embodiment, the

mally preferred.

ity from the system. In another embodiment, the compressor

is poWered by an engine operating on product gas or steam
generated from heat from the synthesis reactor 16.
[0055] The syngas feed 30 from compressor 26 may be
combined With recycled gas 32 that has been compressed to
the approximate pressure of the syngas feed 30 by compressor
34. In the embodiment shoWn in FIG. 1, the combined gas

[0049]

In addition, the gases leaving the syngas generator

are normally in excess of 10000 C. and need to be cooled

doWn before they are introduced to the catalytic reactors 28.

Generated electricity may be needed for certain parts of the

syngas generation system including pumps, feedstock han

dling equipment, condensers, precipitators, etc.

compressor 26 can be run With an electric motor and electric

US 2010/0175320 A1

feed enters the temperature controlled reactor vessels 28.

However, the recycled gases 32 could also enter the reaction

vessel 28 separately. Although recycling of gas is shoWn in

the apparatus of FIG. 1 for e?iciency, it Will be seen that some

of the desired liquid products can be produced With a single

pass through the reactor 28.

[0056]

The pressurized feed syngas and recycle gas streams

30 are fed into at least one synthesis reactor 28 or a series of

reactors as shoWn in FIG. 1 and FIG. 2. Catalyst reactors 28

may be in parallel or in series. In one embodiment, reactors

containing different catalyst compositions are connected in

series to provide sequential reactions.
[0057]

In the preferred embodiment, the reactor 28 is a shell

and tube type synthesis reactor or a ?xed bed reactor. In a shell

Jul. 15,2010

[0065] (3)A second hydrogenation catalyst composed of

CuiZn, Mo, Ni, or Fe.
[0066] The synthesis reactions in reactor 28 primarily con
vert the CO and H2 to desired products depending on the
selection of the catalysts. The amount of gas converted is
dependent on the activity of the catalyst and the space veloc
ity of the gas along With other operational criteria. In the
preferred embodiment, a CO conversion rate of greater than
15% is desired but rates greater than 50% are optimally pre
ferred. The optimally preferred conversion rate is not achiev
able With certain catalysts.

[0067]

Synthesis may include the generation of gas species

that are not catalytically reactive including CO2 and CH4 and
other gaseous hydrocarbons. These gases may help increase

and tube reactor, the gas ?oWs through tubes that contain the
catalyst that are surrounded by boiling Water, all contained

the energy content of the product gas stream Which is useful

Within the vessel shell. The temperature is controlled by con

trolling the pressure of the boiling Water and steam is pro

synthesis When they are recycled to the reactor 28.

[0068] The temperature, pressure and How of the syngas
stream 30 through the reactors 28 is preferably controlled and
monitored to optimize the reaction conditions Within the reac
tors 28. For example, the reactor vessel 28 may include heat

duced that can be used for energy production or other pro

cesses. Another preferred embodiment includes a ?xed bed
reactor Where coolant ?oWs through tubes in a catalyst bed to
remove reaction heat. Syngas ?oWs across the bed and prod
ucts are removed from the opposite end of the bed. Other
preferred embodiments include a ?uidized bed reactor or a

slurry-type ?xed bed reactor. The design of the reactor is

dependent on the syngas throughput, space velocity, tempera
ture and pressure of the system.
[0058] Each synthesis reactor 28 contains a catalyst or mul

tiple layered catalysts chosen to synthesize the desired liquid

product from the syngas fed into the reactor. To synthesize
methanol, for example, CuiZn based catalysts on alumina

supports are optimally preferred. To synthesize higher alco

hols, particularly ethanol, a supported CuiZn catalyst lay
ered With a Group VIII metal catalyst is optimally preferred.

To synthesize hydrocarbon liquids for diesel fuel production,

for electricity generation. They should not greatly impact

ing or cooling elements that permit the regulation of the

temperature of the gas ?oWing through the reactor vessel 28
Within the desired range of temperatures that Will optimize
the reactions. The reaction vessel 28 may also have tempera
ture and pressure monitors to alloW the regulation of the
temperature and pressure of the gas stream through the reac
tion vessel 28. In one embodiment, the temperature and pres
sure in each of the three stages can be varied.

[0069] For the production of ethanol, for example, the reac

tion temperature Within reactor 28 preferably ranges from
approximately 150 C. to approximately 400 C., With
approximately 180 C. to approximately 325 C. particularly
preferred. When a high reaction temperature is used, the
formation of hydrocarbons as byproducts increases.

a supported Fe based catalyst promoted With Cu and K is

[0070]

optimally preferred. In other preferred embodiments, any

namely approximately 200 pounds per square inch gauge

other catalyst including un-supported, supported, and slurry

phase catalysts that have high selectivity and productivity for

(psig), because desired compounds can be manufactured at

that pressure. HoWever, higher pressures can be utilized in

any desired liquid product can be used. Many other synthe

sizable compounds and catalyst formulations for generating

ferred reaction pressure can vary betWeen approximately 200

those compounds are knoWn to those skilled in the art.

psig and approximately 2500 psig. A reaction pressure rang

[0059]

ing from approximately 500 psig to approximately 1500 psig

One catalyst con?guration in reactor 28 has three

stages and selectively produces ethanol at high yields from

synthesis gas and is illustrated in Example 2 beloW. In this
embodiment, syngas is directed over a ?rst catalyst con?g

ured to promote carbon monoxide hydrogenation. The hydro

For some reactions the reactor pressure can be loW,

order to increase the space/time yield. Therefore, the pre

is particularly preferred.
[0071]

The feed rate of the reactant material gas relative to

the volume of catalyst (also knoWn as the gas hourly space

velocity, GHSV, expressed under normal conditions of 0 C.

catalyst that is con?gured to promote hydrogenation of acid

and aldehyde byproducts to alcohols. The reactions prefer
ably occur under conditions of super-atmospheric tempera

and 0 psig) is preferably betWeen 100 and 40,000 hr-l (recip

rocal hours) and is preferably adjusted for each catalyst com
ponent and the reaction conditions to optimize production of
the desired liquid material. Increasing the space velocity can
increase yield and selectivity of the desired products but
reduces the carbon conversion, requiring more recycling of

ture and pressure.

the gas.

genated gas from the ?rst catalyst then reacts With a second

catalyst con?gured to promote alcohol homologation. There

after, the gas from the second catalyst reacts With a third

[0060]

In one illustrative embodiment, the reactor 28 is

packed successively With three layers of catalysts:

[0061] (1 ) A hydrogenation catalyst containing CuiZn,

Mo, Ni, or Fe;

[0062] (2) A carbonylation catalyst containing:

[0063] (a) A Group VIII metal or mixture of Group
VIII metals;
[0064] (b) A co-catalyst metal of yttrium, a lanthanide
and/ or actinide series metal or mixtures thereof; and

[0072]

It can be seen that the reaction conditions can be

regulated to maximize the reaction ef?ciencies of the cata

lysts and products that are selected. Additionally, gas treat
ments devices such as scrubbers may be used to remove

unWanted components of the syngas or recycled gas such as

carbon dioxide or hydrogen sul?de. These treatment devices
can be placed in the gas lines in parallel With the reactors or in
series upstream or doWn stream from the reactors 28.

[0073] Afterpassing though the catalysts in reactors 28, the

outlet stream of gaseous products 36 is directed to the gas/

US 2010/0175320 A1

Jul. 15,2010

liquid separator 38. The gas-liquid separator 38 is preferably

previously, that can drive a steam turbine to generate electric

a condenser but may be any other gas-liquid separator known

in the art. The separated liquid products 40 are collected and

ity for the system or for distribution to the municipal poWer

grid. The multiple sources of electrical poWer generation are

stored for further processing.

more ef?cient for converting the energy from biomass or coal

[0074]

to electricity than direct burning as fuel.

In one embodiment, the separation system is a con

denser using chilled coolant supplied from the Waste heat

from the system. Liquid product is removed from the bottom
of the condenser. In another embodiment, the separator 38
may include some distillation and fractionating equipment to

[0079] Alternatively, steam 58 produced by the engine 54

and the syngas generator 16 can be combined to run one or

separate species based on boiling point.

[0075] Once liquid compounds 40 are separated, the prod

more turbines for electrical generation and the excess system

steam sold to co-located facilities.
[0080] In the embodiment shoWn in FIG. 2, Waste heat from
the engine 54 is used to produce both steam 58 and chilled

uct and un-reacted gases are split into tWo gas streams, the

Water 60 (via an ammonia absorption chiller). Chilled Water

recycle gas 32 and purge gas 42. The recycle gas 32 is mixed

60 and steam 58 generated from the heat sources can be used

With feed syngas 30 from a syngas generator 16 and then

for the process heat and chilling requirements for the system

recycled through the catalyst, resulting in additional CO and

H2 conversion to liquid product 40. The remaining gases 36
emerging from the gas/ liquid separator 38 are preferably
recycled for several cycles by compressing the gas stream

and are merchantable to a local cogeneration host.

[0081]

An automatic process controller subsystem 52 With

controller computer 62 and multiple system and subsystem

sensors monitor the gas composition to control and optimiZe

With compressor 34 as needed to approximately match the

pressure of the syngas feed stream 30 entering the reactors 28.
Valve 44 can be used to direct gas that has been cycled
through the reactors 28 several times to an exit line feed of
purge gas 42. It Will be seen that the cycling of gases through
the reactor effectively concentrates some of the useful gases
such as methane that are produced by the process or are
present in the syngas feed 30. Gas products 42 can be burned

the production processes from syngas generation to synthesis

and electricity generation. For example, continuous gas com
position and How analyZers 22, 64 monitor the gas at multiple
points in the system, preferably after the syngas generator and
before liquid separation. Temperature and pressure sensors

as a source of heat, electrical generation, or can be processed

further as an additional feedstock for other chemical produc
tion. The gas recycle rate can be varied from 0 to 99%. LoWer

recycle, H2 makeup gas, and other operating conditions to

optimiZe the performance of the reactor 28 catalyst and the
electricity generator 54. The computations are preferably

recycle rates favor more electricity production While higher

rates favor liquid product production. The recycle gas 32 is
preferably maintained at elevated pressure but may require

based on chemical thermodynamic and energy models and

some additional compression to compensate from pressure

[0083] The process controller sends control signals to auto

mated valves, the hydrogen generator and the syngas genera

drop through the reactor/ separator system With compressor

34.

[0076]

Turning noW to FIG. 2, the syngas production sub

may also be used at different points in the system to continu

ously monitor reactor and line conditions.
[0082] The process controller 62 computes the amount of

advanced learning algorithms (e.g. neural networks) pro

grammed into the controller system.
tor to alter operating conditions to control the gas composi
tion. LikeWise, compressors and temperature control devices

system 14 and the liquid material production subsystem 12

and associated sensors are controlled by the controller com

are integrated With an electrical generation subsystem 50 and

controller subsystem 52 in the embodiment shoWn. The con
trol subsystem 52 is connected to each of the subsystems to
monitor and control the overall system 10. The production of
gas, liquid material, electricity and steam can be optimiZed
and controlled.

puter 62 to maintain optimum pressure, temperature and How

[0077] In the embodiment shoWn schematically in FIG. 2,

the purge gas 42, consisting primarily of CH4 and other com
bustible product gases and CO2 at high recycle rates, is used
to produce process energy and electricity generation. The
stream of purge gas 42 can be divided and a portion 46 of the
gas can be used to supply process energy for the syngas

generator as described earlier. The second portion 48 and

majority of the gas is delivered to an engine/ generator 54 in
the preferred embodiment. Methane rich purge gas 42 may
alternatively be a source of hydrogen and carbon monoxide

With further processing (not shoWn).

rates of syngas over the catalysts in the reactors 28. Accord

ingly, the controller subsystem 52 can maximiZe the output

production of electricity and liquid products as Well as the

ef?ciency of each of the subsystems through monitoring and

controlling gas production and reaction conditions.
[0084]

In use, the embodiment of FIG. 2 provides a con

tinuous input and output system that utiliZes carbonaceous

fuel and produces electricity, liquid products, steam and

chilled Water. A carbonaceous fuel 18 is continuously fed into
a syngas generator 16. The syngas generator 16 includes

technologies that convert carbonaceous fuels (e.g. agricul

tural, forest and municipal Waste; natural gas, coal, oil shale
and oil sands) into syngas such as pyrolysis, gasi?cation,
reforming, catalysis and other relevant processes. The syngas
20 is composed primarily of CO, H2, and lesser amounts of
CO2 and CH4. The syngas generator system 14 may also

It can be seen that electricity can be produced by the

include various gas cleanup devices to remove contaminants

electrical generation subsystem 50 in tWo Ways. First, elec

tricity can be produced by burning gas directly as fuel in a

from the syngas including scrubbers, precipitators, etc. In this

embodiment, process electricity 68 and product gas 42 can be
used to operate the syngas generator system 14. In other

[0078]

turbine or engine 54 that turns generators 56 to produce

electricity as in a conventional natural gas ?red generator. The

embodiments, additional energy can be supplied to the syngas

second source of electrical production comes from steam 58

generator from an external fuel source.

produced from the hot exhaust gases from the turbine or

engine 54, Which can be used to turn a steam turbine genera

[0085] Syngas exits the syngas generator 16 and may be

combined With a quantity of hydrogen gas from a hydrogen

tor. Electricity can be produced by the Whole system in a third

Way from steam produced by the syngas generator, described

generator 24. In this embodiment, the hydrogen generator 24

is an electrolysis generator that utiliZes process electricity 68

US 2010/0175320 A1

to generate H2 gas from Water. The hydrogen is combined

With the syngas 20 to adjust the ratio of H2 to CO for preferred

catalyst performance. The amount of hydrogen added is

determined by monitoring the gas composition With continu
ous gas analyzers 22 and 64 and comparing that composition
With the optimum composition from algorithms and informa
tion from the process control computer subsystem 52.
[0086] A compressor 26 increases the pressure of the com
bined feed gas to reaction pressure. In one embodiment, the
compressor 26 is poWered With process electricity 68 or from

Jul. 15,2010

quanti?es the amount and composition of the gas exiting the

catalysts 28 after the pressuriZed gas/ liquid separator 38. The

process controller 62 computes the amount of gas to recycle
based on a process model and sends a control signal to the

split valves 44 and 66. The process controller 62 also com

putes the amount of makeup H2 needed for optimal catalyst

performance and sends a control signal to the hydrogen gen
erator 24.

steam/ electricity generated from the exothermic reaction of

the catalyst reactors in the alternative. In other embodiments,

[0092] The invention may be better understood With refer

ence to the accompanying examples, Which are intended for
purposes of illustration only and should not be construed as in
any sense limiting the scope of the present invention as

the compressor 26 or 34 can be poWered by syngas or an

external fuel source. The feed gas 30 is combined With

de?ned by the claims appended hereto. The folloWing

examples demonstrate the productivity and e?iciency of this

recycled gas 37 and the combined stream enters the catalyst

invention for the conversion of syngas to various liquid fuel

reactors 28. The catalyst reactors 28 can be any type of pres

products. These examples are shoWn utiliZing particular

suriZed catalytic system. The catalyst reactors 28 contain a

catalyst or multiple catalysts that have been selected for the
conversion of syngas to products such as alcohols, gasoline

illustrations in order to make the present invention more

understandable.

and diesel fuels. The input gas 30, containing primarily CO,
H2, CO2 and CH4, is partially converted to the products and

EXAMPLE 1

inputs, formulations, reaction conditions, and ef?ciencies as

other non-reactive gases Within the catalyst reactors 28.

[0087] The catalyst output gases 36 are directed to a gas/

Production of Syngas and Fuels

liquid separator 38 that operate at pressures just beloW that of

the synthesis catalyst reactor 28 operating pressures. In this
embodiment, liquids are condensed by reducing the tempera

is operated in the absence of oxygen or air to produce syngas

With an average molar composition of 35% H2, 28% CO, 18%

ture With chilled Water from chiller 60. These liquids 40 are

CO2 and 18% CH4 (Table 1).

directed to product storage tanks from Which they can be

[0093] In Example 1, a pyrolysis/steam reforming system

at valve 44 and a portion is re-compressed up to the operating

[0094] Continuous Gas AnalyZers (22 and 64) in FIG. 1 and

FIG. 2, speci?cally mass spectrometers in this example, are
used to obtain real-time measurements by monitoring the
molecular peaks of the gas-phase species listed in Table 1
before (BC) and after the catalyst reactors (AC). The syngas
generator for this example utiliZes pyrolysis/ steam reforming

pressure of the synthesis catalysts by compressor 34, and

thermochemical process in the absence of oxygen or air.

distributed. In other embodiments, liquids 40 may be subject

to on-site or off-site Water removal, separation and re?nement

if needed to provide puri?ed products.

[0088] Gases from the gas/liquid separator 38 may be split
recycled back to the catalyst reactor 28 to further convert the

Since nitrogen has the same nominal mass as carbon monox

reactive species. The other portion, called the product or

ide (m/e: 28) and oxygen has the same nominal mass as

purge gas 42, is directed to valve 66, Where a fraction 46 is

directed to the syngas generator 16 to provide process energy

methanol (m/e: 32), the presence of nitrogen and oxygen

and the other fraction 48 is directed to compression ignition

bon monoxide and methanol. Therefore, the initial concen

gas engines or turbines 54. The mechanical energy from each

gas engine or turbine operates a generator 56 to produce
electrical poWer and heat. Compared to the original syngas,
this product gas 42 contains higher concentrations of com

trations of the gas-phase species, listed under FPS Operation

(Initial Conditions), Were measured using gas chromatogra
phy and gas chromatography/mass spectrometry. It Was
found that nitrogen (0.4 Mole %) and oxygen (0.05 Mole %)

bustible, but non-catalytically reactive gases (like CH4). This

Were very loW and therefore these species Will not interfere
With the carbon monoxide and methanol measurements using
the on-line mass spectrometer. Tables 1 and 2 illustrate the
results for the process optimization of syngas to alcohol con

enriched gas improves the thermal energy conversion e?i

ciency of gas engines and gas turbines.
[0089] Electrical poWer from the generators 56 is con
nected to an electrical distribution system 68. A portion of the
electrical poWer may be utiliZed by the hydrogen generator
process 24 and the net poWer is supplied to an external grid as
an additional product.

[0090]

In this embodiment, heat from the engine and engine

exhaust is converted to chilled Water 60 and steam 58 to be

utiliZed in the process or co-located cogeneration facilities.

[0091] A process controller 52 subsystem controls the pro

duction process. This process controller is typically computer
based, but analog controllers can also be utiliZed alone or in

combination With computer based systems. In FIG. 2, the

process controller 62 controls the gas recycle at valves 44 and
66 and the addition of H2 to the gas feed to the catalyst
reactors 28 to optimiZe performance. A continuous gas ana

lyZer 22 quanti?es the amount and composition of the syngas

from the syngas generator 16 and reports this information to
the process controller 62. Another continuous gas analyZer 64

could cause an error in the quantitative measurement of car

version ef?ciency and ethanol/methanol production selectiv

ity using a MoS2/K2CO3 :La2O3/Y2O3 catalyst as an example.
This example represents one gas recycle.
[0095] The initial catalyst conditions are presented in Table
1. The hydrogen generator Was used to add enough extra
hydrogen to increase the H2/CO from 1.25 to 1.69. It is
observed that hydrogen and carbon monoxide is decreased as
a result of reactions over the catalyst With the subsequent
production of methanol, ethanol and propanol. The CO con
version e?iciency is 30.8% and alcohol product consisted of
48.9 Wgt. % ethanol/48.5 Wgt. % methanol and 2.6 Wgt. %

propanol.
[0096] After 60 minutes of data collection, changes in cata
lyst process conditions, the computer model determines that
the space velocity should be decreased from 9000 hrl to
5500 hr-1 and the catalyst reactor temperature increased to
5000 F. This change results in a slight decrease in the CO

US 2010/0175320 A1

Jul. 15,2010

conversion e?iciency (30.8% to 29.2%) but the selectivity of

ciencies to approximately 48%, resulting in greater product

ethanol to methanol is increased (57.5 Wgt. % ethanol/37.9

Wgt. % methanol) With a small increase in propanol (4.6 Wgt.

yields and concurrent increased economic bene?ts.

EXAMPLE 3
Production of Mixed Alcohols

%).
[0097] After another 90 minutes of process changes in cata
lyst conditions, the computer model determines that the maxi
mum CO conversion ef?ciency and ethanol/methanol selec

tivity has been achieved. The optimum CO conversion

ef?ciency is 36.0%, and the alcohol selectivity is 66.1 Wgt. %
ethanol/ 28.3 Wgt. % methanol) With an acceptable increase in

propanol (5.6 Wgt. %).

[0103]

80% Ethanol, 15% Methanol, 5% C3+Alcohols

This example uses a multi-layered catalyst combi

nation based on a promoted CuiZn and a promoted Group

VIII metal catalyst to produce a mixture of alcohols contain

ing primary ethanol.

[0104] Table 4 shoWs the operating conditions for this sys
tem including catalyst pressure, reactor temperature, CO con

version, and selectivity. In addition, this table summarizes the

[0098] This computer-controlled optimiZation process is

resulting outputs and ef?ciencies for this system With a syn

gas input of 500,000 SCF per hour. The productivity of the

not limited to the production of ethanol but equally applicable

to the production of other fuels and chemical feedstocks such
as other alcohol fuels, diesel, dimethyl ether and gasoline.
[0099] In the next three examples, the output of a plant that

plant is shoWn for three different recycle rates (0%, 75%, and
90%) to demonstrate the range of operating conditions and

generates and converts a syngas feed of 500,000 standard

cubic feet (SCF) per hour is used. The average molar compo

of ethanol and electricity seen in Example 3 is similar to that

shoWn Example 2 for a product stream With a higher energy
density. This product stream of ethanol may be more suitable

sition ofthe syngas is 38% H2, 23% CO, 23% CO2 and 15%
CH4. For comparative purposes, it is estimated that this syn
gas could be generated from pyrolysis/ steam reforming of 10
tons per hour of 8500 BTU/lb Wood Waste, or pyrolysis/ steam
reforming of 9 tons per hour of 9500 BTU/lb of sub-bitumi

nous coal, or partial oxidation/steam reforming of 150,000

SCF per hour of stranded natural gas at 1000 BTU/SCF. For

these examples it is assumed that the syngas generation unit

must be supplied With supplemental product gas and electric
ity resulting in an overall thermal ef?ciency of 70%.
[0100] Examples 2 through 4 demonstrate that the system
described in this invention can give commercially reasonable

product mixes.
[0105] The productivity and ef?ciency for the production

for fuel applications or more desirable for economic reasons.

EXAMPLE 4

Production of Diesel Syncrude

[0106] LoW temperature Fischer-Tropsch synthesis cata

lysts have been developed to produce liquid hydrocarbons
useful for producing high quality diesel fuel and other prod
ucts. Both Fe and Co based catalysts have been used for this
purpose. For this example, a Fe based catalyst promoted With
K and Cu is used in a tubular-type reactor for the production

of primarily C5+ ole?ns and paraf?ns. Table 4 shoWs the

operating conditions, the resulting outputs and ef?ciencies

EXAMPLE 2

for this system With a syngas input of 500,000 SCF per hour.
The productivity of this system is shoWn for three different
recycle rates to demonstrate the range of product mixes.
[0107] It can be seen in this example that because of the
high conversion rate of CO over the catalyst, feWer recycle
loops are needed to produce an ideal production level of fuel.
The combined thermal ef?ciency of 47% for the integrated
process results in greater product yields and concurrent eco
nomic bene?ts than the current best available technologies.
These three examples demonstrate clear commercial bene?ts

Production of Methanol

of this invention for the combined production of liquid fuels,

electricity and heat from carbonaceous feedstocks.

quantities of products using conventional catalysts. Further,

this system uses a minimal amount of capital equipment

relative to other systems for producing similar liquid fuel

products at much larger scales not viable for small and
medium siZed distributed systems.

[0108] Although the description above contains many

[0101]

In order to demonstrate the production of one liquid

product and electricity With the system shoWn schematically

details, these should not be construed as limiting the scope of

the invention but as merely providing illustrations of some of

duce methanol. The catalyst used in the synthesis reactor 28

the presently preferred embodiments of this invention. There

fore, it Will be appreciated that the scope of the present inven
tion fully encompasses other embodiments Which may

Was a CuiZn based catalyst used for methanol synthesis.

become obvious to those skilled in the art, and that the scope

Table 3 shoWs the operating conditions for this system includ

of the present invention is accordingly to be limited by noth

ing other than the appended claims, in Which reference to an
element in the singular is not intended to mean one and only

in FIG. 2, the catalyst of the reactor 28 Was selected to pro

ing catalyst pressure, reactor temperature, CO conversion,

and selectivity. In addition, Table 3 summarizes the resulting
outputs and ef?ciencies for this system With a syngas input of
500,000 SCF per hour. The productivity of the plant is shoWn

for three different recycle rates (0%, 75%, and 90%) to dem
onstrate the range of operating conditions and product mixes.
[0102]

It can be seen that the synthesis of liquid fuels alone

gives loWer (9%-37%) thermal conversion ef?ciencies that

are particularly pronounced at loWer recycle rates. The com

bined production of fuel and electricity also provides a higher

one unless explicitly so stated, but rather one or more.All

structural, chemical, and functional equivalents to the ele

ments of the above-described preferred embodiment that are
knoWn to those of ordinary skill in the art are expressly
incorporated herein by reference and are intended to be

encompassed by the present claims. Moreover, it is not nec

essary for a device or method to address each and every

problem sought to be solved by the present invention, for it to

be encompassed by the present claims. Furthermore, no ele

combined liquid fuel synthesis and electricity generation

ment, component, or method step in the present disclosure is

intended to be dedicated to the public regardless of Whether
the element, component, or method step is explicitly recited
in the claims. No claim element herein is to be construed
under the provisions of 35 U.S.C. 1 12, sixth paragraph, unless

described in this example increases thermal conversion e?i

the element is expressly recited using the phrase means for.

thermal ef?ciency than seen With the direct production of

electricity from the syngas, Which is about 28% When using

the best available technologies for electricity production. The

US 2010/0175320 A1

Jul. 15, 2010

TABLE 1
Gas Composition (Mole %)

Gas-Phase
Species

MW

Hydrogen
Methane
Carbon
Monoxide
Nitrogen
Ethane
Methanol
Oxygen
Carbon
Dioxide
Ethanol
Propanol
Benzene
Toluene
Total

FPSl

FPS

FPS

Operation

Operation

Operation

(Initial Conditions)

(60 min)

( 150 min)

SI*

BC**

AC***

BC**

AC***

BC**

AC**

2
16
28

35
18
28

44
15
26

31
15
18

42
18
24

29
19
17

41
18
25

27
19
16

28
30
32
32
44

0.4
0.01
0.00
0.05
18

0.4
0.01
0.00
0.05
15

0.4
0.01
10.7
0.00
16

0.5
0.01
0.00
0.00
16

0.5
0.01
9.2
0.00
16

0.5
0.01
0.00
0.00
16

0.05
0.01
7.5
0.00
17

46
60
78
92

0.00
0.00
0.01
0.00

0.00
0.00
0.01
0.00

7.5
0.3
0.01
0.00

0.00
0.00
0.02
0.00

9.7
0.6
0.02
0.00

0.00
0.00
0.03
0.00

12.2
0.8
0.03
0.00

99.50

100.50

98.9

100.5

101.0

101.5

99.6

*Sl: Syngas Input;

**BC: Before Catalyst Reactor;
***AC: A?er Catalyst Reactor

lFPS Operation (Initial Conditions) Temperature: 450 F.; Space Velocity: 9000 hrl; Pressure: 750 psi
2FPS Operation (60 min) Temperature: 500 F.; Space Velocity: 5500 hrl; Pressure: 750 psi
3FPS Operation (150 min) Temperature: 575 F.; Space Velocity: 4000 hrl; Pressure: 650 psi

TABLE 2

TABLE 3-c0ntinued

Results for the Process Optimization of Syngas to Alcohol

Conversion Ei?ciency and Ethanol/Methanol Production

Example 2: Production OfMethanol and El?cmclty

Selectivity Using a MoS2/K2CO3:La2O3/Y2O3

Catalyst in the Fuel Production System (FPS)
FPS

op?mtion

FPS

FPS

(Initial

Operation

Operation

Conditions)

(60 min)

(150 min)

30.8

29.2

36.0

Parameter/Product

Optimized

Ei?ciency (%)

CO Conversion

'

'd

Liqui Fue On y

Liquid Fuel + Electricity

24

37

33

41

48

Ei?ciency (%)
Ethanol (Wgt. %)

48.9

57.5

66.1

Methanol (Wgt. %)

48.5

37.9

28.3

2.6

4.6

5.6

Propanol (Wgt- %)

TABLE 4
_

Example 3. Production of Mixed Alcohols and Electricity

Operating Conditions:
Synthesis Catalyst
Pressure (psi)

TABLE 3
Example 2: Production of Methanol and Electricity

Temperature (0 F.)

Layered CuiZn and Group VIII

750
500

CO Conv?rsion (%)

30

Selectivity (mol % C):

Operating Conditions:
Synthesis Catalyst
Pressure (psi)

Promoted CuiZn
700

Temperature (0 F.)

510

CO Conversion (%)

15

Mixed Alcohols*

74

CH4
CO2

20
5
Plant Productivity:

Selectivity (mol % C):

Recycle Rate (%)
Methanol

95

Mixed Alcohols

CH4

(gal/hr)

CO2

Net Electricity (MW)

75

90

260

548

703

9.6

6.0

4.1

Ei?ciency (%)
Plant Productivity:
Recycle Rate (%)
Methanol (gal/hr)
Net Electricity

0
230
12_1

75
632
8_6

90
975
5_6

Liquid Fuel Only

13

27

37

Liquid Fuel + Elec.

32

39

45

*Product distribution is 80% Ethanol, 15% Methanol, 5% Other Alcohols

US 2010/0175320 A1

Jul. 15,2010
10
controlling temperature, pressure, space velocity, chemical
composition and recycle rates of said pre- and post cata

TABLE 5

lyst synthesis gas streams.

Example 4: Production of Diesel Syncrude and Electricity

Operating Conditions:

5. A process as recited in claim 1, further comprising:

converting carbon dioxide gas in said synthesis gas stream
to carbon monoxide gas.

Synthesis Catalyst
Pressure (psi)

Fe Promoted with Cu and K

300

Temperature (0 F.)

450

CO Conversion (%)

80

6. A process as recited in claim 1, wherein said hydrogen

source is generated by electrolysis of water with electricity

generated by the system.

Selectivity (mol %

7. A process as recited in claim 1, further comprising:

producing steam from excess heat from combustion, cata

C :

Liquid Hydrocar-

82

lytic reactor and synthesis gas production to produce

5
12

generating electricity from the steam, thereby increasing

bons*
CH4
CO2

steam; and

the energy ef?ciency of the entire system.

Plant Productivity:
Recycle Rate (%)
Diesel Syncrude

0
435

75
511

90
530

(gal/hr)
Net Electricity (MW)

8. A process as recited in claim 1, further comprising:

using a portion of the excess heat from combustion of said

unreacted synthesis gases for gasi?cation of carbon

aceous feedstock.

4.6

3.1

2.7

Efficiency (%)
Liquid Fuel

34

40

Liquid Fuel + Elec.

43

46

41
47

*Product distribution is 85% C5+ hydrocarbons, 60-80% ole?nic, at 140,000 BTU/gal, well
suited for high quality low-sulfur diesel fuel

What is claimed is:

1. A process for the continuous production of electricity,

heat and syngas derived products, comprising:

9. A process as recited in claim 1, further comprising:

using a portion of the excess heat from combustion of said
unreacted synthesis gases for an absorptive chiller used
to provide chilled ?uids for a condenser to separate
reaction products from a post catalyst gas stream.
10. A process as recited in claim 1, further comprising:
controlling compressors, valves and ?ow rates of gas with
a process controller and sensors.

11. A process for the continuous production of electricity,

heat and syngas derived products, comprising:

converting biomass or fossil fuels to a stream of synthesis

gases;

generating synthesis gas stream from a carbonaceous feed

analyzing characteristics of said stream of synthesis gases;

supplementing said stream of synthesis gases with hydro

reacting the synthesis gas stream with catalysts selected to

gen gas from a source of hydrogen gas to produce a

supplemented stream of synthesis gas with a regulated

composition;
reacting the supplemented synthesis gas stream with cata
lysts selected to convert carbon monoxide and hydrogen
to reaction products to produce a stream of reaction

products and unreacted synthesis gases;

separating reaction products from the unreacted synthesis
gases; and

combusting the unreacted synthesis gases to produce elec

tricity and heat.
2. A process as recited in claim 1, further comprising:
mixing a portion of the unreacted synthesis gases with said

supplemented stream of synthesis gases; and

recycling said mixed gas stream through the catalyst for at
least one cycle,

wherein the conversion ef?ciency of reactive gases to prod

ucts is maximized.

3. A process as recited in claim 1, further comprising:

monitoring of the characteristics of the pre- and post-cata

lyst gas stream;

optimizing a ratio of recycle gas with synthesis gas to
provide a synthesis gas stream that has approximately

the highest reaction ef?ciency with the catalysts; and

concentrating said recycled unreacted gas stream gases
prior to combustion.
4. A process as recited in claim 3, further comprising:
using software models to analyze said monitored gas char

acteristics to establish optimum operating conditions;

and

stock;
convert carbon monoxide and hydrogen to reaction
products to produce a stream of reaction products and

unreacted synthesis gases;

separating reaction products from the unreacted synthesis
gases;

splitting said unreacted synthesis gases into two streams;

recycling a portion of unreacted synthesis gases through
said catalysts for at least one cycle;
combusting a portion of the unreacted synthesis gases;
monitoring pressure, temperature, gas composition and
?ow rates of the synthesis gas ?ow and recycled synthe
sis gas ?ow with sensors;

controlling the pressure, temperature, gas composition and

?ow rates of the synthesis gas ?ow and recycled synthe
sis gas ?ow and output of reaction products and electric
ity with a process controller; and
producing steam with excess heat from a gas combustion

chamber.
12. A process as recited in claim 11, further comprising:

analyzing continuously said stream of synthesis gases and

recycled gases; and
supplementing said stream of gases with hydrogen gas
from a source of hydrogen gas to produce a supple
mented stream of synthesis gas with a regulated ratio of
hydrogen to carbon monoxide.

13. A catalytic reactor, comprising:

a reaction vessel with at least one reaction chamber and an

intake duct and an output duct;

a ?rst hydrogenation catalyst;

a carbonylation catalyst; and
a second hydrogenation catalyst,

US 2010/0175320 A1

wherein gas containing carbon monoxide and hydrogen

entering through said intake duct can pass sequentially
through each catalyst and through the output duct.
14. A catalytic reactor as recited in claim 13, further com

prising:
means for heating gasses Within said reaction Vessel.
15. A catalytic reactor as recited in claim 13, further com

Jul. 15,2010

17. A catalytic reactor as recited in claim 13, Wherein said

?rst hydrogenation catalyst is a catalyst selected from the

group of catalysts consisting essentially of Cu, Zn, Mo, Ni, or

Fe.
18. A catalytic reactor as recited in claim 13, Wherein said

hydrogenation catalyst further comprises an alkali metal pro

moter, selected from the group of promoters consisting essen

tially of Ti, Zr, Pd, and Mn.

19. A catalytic reactor as recited in claim 13, Wherein said

prising:

carbonylation catalyst comprises at least one Group VIII

a catalyst support carrier.

16. A catalytic reactor as recited in claim 15, Wherein said
support carrier is a carrier selected from the group of carriers

metal and at least one co-catalyst.

20. A catalytic reactor as recited in claim 13, Wherein said

consisting essentially of aluminum oxide, silica, a Zeolite,

titanium oxide, metal and clay.

co-catalyst comprises yttrium metal, a lanthanide series metal

or an actinide series metal.
*