U.S. patent application number 14/512799 was filed with the patent office on 2015-05-07 for process and system for converting waste to energy without burning.
The applicant listed for this patent is Intellergy, Inc.. Invention is credited to Terry R. Galloway.
Application Number | 20150122243 14/512799 |
Document ID | / |
Family ID | 47068372 |
Filed Date | 2015-05-07 |
United States Patent
Application |
20150122243 |
Kind Code |
A1 |
Galloway; Terry R. |
May 7, 2015 |
PROCESS AND SYSTEM FOR CONVERTING WASTE TO ENERGY WITHOUT
BURNING
Abstract
This invention relates to a power recovery process in waste
steam/CO.sub.2 reformers whereby a waste stream can be made to
release energy without having to burn the waste or the syngas. This
invention does not make use of fuel cells as its critical component
but makes use of highly exothermic chemical reactors using syngas
to produce large amounts of heat, such as Fischer-Tropsch. It also
relates to control or elimination of the emissions of greenhouse
gases in the power recovery process of this invention with the goal
of producing energy in the future carbonless world economy. A New
Concept for a duplex kiln was developed that has the combined
functionality of steam/CO.sub.2 reforming, heat transfer, solids
removal, filtration, and heat recovery. New methods of
carbon-sequestering where the syngas produced by steam/CO.sub.2
reforming can be used in Fischer-Tropsch processes that make
high-carbon content compounds while recycling the methane and
lighter hydrocarbons back to the reformer to further produce syngas
at a higher H.sub.2/CO ratio.
Inventors: |
Galloway; Terry R.;
(Berkeley, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Intellergy, Inc. |
Berkeley |
CA |
US |
|
|
Family ID: |
47068372 |
Appl. No.: |
14/512799 |
Filed: |
October 13, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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12287996 |
Oct 14, 2008 |
8858900 |
|
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14512799 |
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Current U.S.
Class: |
126/263.01 ;
422/187 |
Current CPC
Class: |
C10G 2/332 20130101;
B01J 2208/00309 20130101; Y02P 20/129 20151101; C01B 2203/043
20130101; C01B 2203/0894 20130101; C10K 1/04 20130101; C01B
2203/0216 20130101; C01B 3/48 20130101; C10K 1/024 20130101; B01J
8/10 20130101; C10G 2/32 20130101; C10J 3/84 20130101; C10K 3/04
20130101; B01J 2208/00752 20130101; C10G 2300/4081 20130101; C10K
1/002 20130101; B01J 8/006 20130101; B01J 2208/0053 20130101; B01J
2219/0004 20130101; Y02P 30/40 20151101; C10J 2300/1246 20130101;
C10G 2300/4043 20130101; C10G 2/30 20130101; Y02P 20/145 20151101;
C01B 2203/148 20130101; F24V 30/00 20180501; C10J 2300/1853
20130101; C01B 3/34 20130101; C10J 2200/09 20130101; C01B 2203/0222
20130101; B01J 8/0271 20130101; B01J 2208/00415 20130101; C10J 3/20
20130101; Y02P 30/00 20151101; C01B 2203/0475 20130101; C01B
2203/062 20130101; Y02E 50/10 20130101; C10K 1/32 20130101; C10J
3/007 20130101; B01J 8/009 20130101; C01B 2203/0283 20130101 |
Class at
Publication: |
126/263.01 ;
422/187 |
International
Class: |
F24J 1/00 20060101
F24J001/00; C10J 3/20 20060101 C10J003/20; C10J 3/84 20060101
C10J003/84 |
Claims
1. A system consisting of an improved rotary kiln for carrying out
steam/CO.sub.2 reforming, where the preferred features of waste
volatilization, steam/CO.sub.2 reforming, gas heat exchange,
filtration and solid separation are combined into a single duplex
kiln that uses in the primary region a heated hollow flight screw
to begin the endothermic steam/CO.sub.2 reforming of the biomass or
waste feedstock, where the off-gases are carried into a second
region where inductively-heated annular surfaces radiatively heat
the gases to 800-1050.degree. C. (1470-1920.degree. F.) and
particulate is removed so that these hot gases can pass now
counter-currently through the central shaft and then through the
hollow flight screw internal cavities to supply the reforming heat
needed to do the endothermic chemistry and cool the syngas for kiln
exit.
2. A system in 1 that includes spiral vanes to carryout a cyclonic
separation of entrained solids so that the syngas produced has high
quality so to avoid detrimental effects of fuel cell poisoning
arising from undesirable constituents in the waste.
3. A system in 1 that includes an internal high-temperature porous
ceramic or metal filter cartridge to further remove entrained
solids so that the syngas produced has high quality so to avoid
detrimental effects on downstream process units of catalyst
poisoning arising from undesirable constituents in the waste.
4. A process that provides the interface between a steam/CO.sub.2
reforming waste conversion system generating syngas and a
Fischer-Tropsch Unit that uses said syngas that makes paraffin wax
product for carbon sequestration while recycling the light
hydrocarbons off of the Fischer-Tropsch Unit, consisting of
hydrogen, CO, CO.sub.2, methane, ethane, propane, etc. to avoid
their emissions as powerful greenhouse gases and also recycling the
lighter hydrocarbons to help maintain a higher H.sub.2/CO ratio of
the syngas. The Fischer-Tropsch unit, which is exothermic, produces
a large steam flow for turbine-generation of electricity and, thus,
replaces the need for a fuel cell. This process method destroys the
waste stream while at the same time the syngas is made to release
energy without having to burn the waste or the syngas.
5. A system of 1 where the kiln residue can be converted into
carbon-containing fertilizer, and a carbon-sequestering,
high-carbon content product of important commercial value.
6. System of 4 where a Fischer-Tropsch synthesis reactor system is
used to produce a high carbon content compound that can be sold
into markets where it is never burned in its life cycle and
therefore serves as a carbon sequestering agent and where the
Fischer-Tropsch overhead stream containing hydrogen, CO, CO.sub.2,
methane, ethane and light paraffins are recycled back to the
steam/CO.sub.2 reformer in order to make use of their high hydrogen
content to achieve the more desirable H.sub.2/CO ratio around
1.0.
7. A system of 4 where a Fischer-Tropsch unit combined with a
parallel shift converter/pressure-swing absorption unit to
accomplish the conversion of the syngas to commercially-marketable
hydrogen fuel, ample steam to generate electrical power for the
plant and for export, and a high-carbon content organic product
paraffin that sequesters substantially the carbon in the waste
stream--all without any burning of the waste or the syngas.
8. A system of 7 where the light gases from the Fischer-Tropsch
unit are recycled back to the steam reformer for destruction and
avoiding release to the environment.
9. A system of 7 where carbon dioxide and a portion of the hydrogen
from the Shift and Pressure Swing Absorber units are recycled back
to the steam reformer to adjust the H.sub.2/CO ratio for optimum
utilization in the Fischer-Tropsch unit.
10. A system of 7 where small impurities in the syngas that could
damage the sensitive catalysts in a high temperature fuel cell do
not damage the more robust catalysts (i.e. iron or cobalt-based) in
a Fischer-Tropsch unit.
11. A system of 4 where the best clean-up of syngas impurities
involves a process where there are both a high temperature
filtration step and a sulfur-, chlorine-, and nitrogen containing
compound removal step as well as a chilling and condensation step
downstream which includes a HEP A filter and a guard bed to protect
high temperature fuel cell electrochemical catalysts.
12. A system of 4 where the best clean-up of syngas impurities
involves a process where there are both a high temperature
filtration step and a sulfur-, chlorine-, and nitrogen containing
compound removal step as well as a chilling and condensation step
downstream which includes a HEPA filter and a guard bed to protect
Fischer-Tropsch catalysts.
13. A system of 4 where a Fischer-Tropsch unit that is greatly
simplified because its many tail or overhead streams can be used as
recycle to the steam/CO.sub.2 reforming process.
14. A system of 6 where a heat recovering exothermic reactor that
contains a supported catalyst immersed in water to maintain the
catalyst at a constant temperature by the boiling of the water to
make steam that is used to generate power.
15. A system of 4 where a power recovery system that involve the
combined use of a shift and PSA unit as well as the Fischer-Tropsch
unit to make best use of recycle streams and waste heat.
16. A system of 14 where an exothermic reactor consists of a
Fischer-Tropsch reactor.
17. A system of 14 where an exothermic reactor consists of a
methanol synthesis reactor.
18. A system of 14 where an exothermic reactor consists of a
methanation reactor.
19. A system of 1 where heat to the kiln sections doing endothermic
steam/CO.sub.2 reforming is supplied by recycling the syngas
through the holoflite screw to heat the waste and do reforming.
20. A system of 4 where hot syngas from a conventional kiln
followed by the steam/CO.sub.2 reformer is heat exchanged with
another inert gas, such as carbon dioxide or air, to heat the kiln
by indirect heating in the oven surrounding rotary kiln tube by
means of a series of injection jets, where gas burners are normally
located.
21. (canceled)
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent
application Ser. No. 12/287,996, filed Oct. 14, 2008, now issued as
U.S. Pat. No. 8,858,900, incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This application involves related subject matter to U.S.
Patent Application No. 60/749,306, was filed Dec. 12, 2005,
incorporated herein by reference.
[0003] The invention relates to a process and system in which a
waste stream can be made to release energy without having to burn
the waste or the syngas and consume oxygen and have large carbon
dioxide emissions. At the same time the waste can be converted into
a carbon-containing fertilizer, hydrogen fuel, and a
carbon-sequestering, high-carbon content product of important
commercial value, such as unsaturated, high-density paraffin.
BACKGROUND OF THE INVENTION
[0004] The process and system for carrying out the steam/CO.sub.2
reforming chemistry to accomplish this has been patented by the
author (U.S. Pat. No. 6,187,465, issued Feb. 13, 2001 and CIP U.S.
Pat. No. 7,132,183, issued Nov. 7, 2006, filed Jun. 23, 2003) and
deals with waste steam/CO.sub.2 reformers interfacing to fuel
cells. And CIP of patent application Ser. No. 10/719,504 (examined
by Ryan/Lewis) filed Nov. 21, 2003 deals with cleaning the syngas
produced in waste steam/CO.sub.2 reformers interfacing to fuel
cells to produce energy without poisoning their sensitive
catalysts.
[0005] There is a great need to destroy a wide range of waste
streams generated around the world and at the same time to convert
this carbonaceous waste into useful hydrogen-rich syngas by two
methods: (1) to drive a fuel cell and (2) to feed a Fischer-Tropsch
unit--both to produce clean energy.
[0006] The challenge and problem with fuel cells has been their
extreme sensitivity to various unknown chemical poisons at parts
per million levels coming from the waste streams from harming the
electrochemical catalysts of the high temperature fuel cells. By
comparison Flory-Huggins catalysts in Fischer-Tropsch reactors
(such as supported iron and cobalt catalysts) are much less
sensitive to poisons than fuel cells and are highly exothermic.
CO+2H.sub.2.fwdarw.1/n(--CH.sub.2--).sub.n(l)+H.sub.2O(l)
.DELTA.H.degree..sub.298=-231.1 kJ/mol
[0007] Conversion of syngas to methanol using copper catalysts in
the gas phase or liquid-phase catalysts are exothermic and also
less sensitive to poisons.
CO+2H.sub.2.fwdarw.CH.sub.3OH(l) .DELTA.H.degree..sub.298=-128.2
kJ/mol
[0008] There is syngas methanation that is highly exothermic:
2CO+2H.sub.2.fwdarw.CH.sub.4+CO.sub.2
.DELTA.H.degree..sub.298=-247.3 kJ/mol
[0009] And there are many other highly exothermic reactions that
can use syngas and preferably produce useful high-carbon content
chemicals of commercial use.
[0010] This thermochemistry is well known (R. F. Probstein & R.
E. Hicks, "Synthetic Fuels," McGraw-Hill, N.Y., 1982, 490 pp.). And
all of these highly exothermic reactors produce high-grade useful
energy. So they all can convert syngas with enough exothermicity to
make large amounts of electricity, steam and heat. Importantly,
these exothermic reactors can substitute very well for fuel cells.
Thus, it is the purpose of this patent to cover methods and process
systems to convert waste to energy without burning the waste but to
sequester the carbon of the waste so carbon gases are not
released
[0011] The composition of the syngas was determined in detail by
the author in a recently completed gas test using the Bear Creek
Pilot plant where solid waste was steam/CO.sub.2 reformed to make
syngas. The syngas composition is shown in Table 1 below.
TABLE-US-00001 TABLE 1 Results from Pilot Plant Gas Test By
Steam/CO.sub.2 Reforming Of Solid Waste H.sub.2 Hydrogen 62.71 vol
% CO Carbon Monoxide 18.57 CO.sub.2 Carbon Dioxide 10.67 CH.sub.4
Methane 7.58 C.sub.2H.sub.6 Ethane 0.48 C.sub.3 TO C.sub.6 Propane
through hexane <0.01 C.sub.6H.sub.6 Benzene <17 ppm COS
Carbonyl Sulfide 4 ppm CS.sub.2 Carbon Disulfide 0.05 ppm H.sub.2S
Hydrogen Sulfide <5 ppm C.sub.10H.sub.8 Naphthalene 2.6 ppb
C.sub.10H.sub.7CH.sub.3 2-Methylnaphthalene ~0.6 ppb
C.sub.12H.sub.8 Acenaphthalene ~0.4 ppb C.sub.12H.sub.8O
Dibenzofuran 0.36 ppb PCDF + PCDD Polychlorinated- 0.0041 ppt TEQ
dibenzofurans + Dioxins
[0012] The pilot process configuration used to conduct these tests
is described in a recent publication (T. R. Galloway, F. H.
Schwartz and J. Waidl, "Hydrogen from Steam/CO.sub.2 Reforming of
Waste," Nat'l Hydrogen Assoc., Annual Hydrogen Conference 2006,
Long Beach, Calif. Mar. 12-16, 2006).
[0013] What has been found experimentally was that the syngas was
very rich in hydrogen and carbon monoxide and also quite pure. For
fuel cells the key poisons, such as carbonyl sulfide, hydrogen
sulfide, carbon disulfide, hydrogen chloride, and polychlorinated
organics were identified. For Fischer-Tropsch, methanol synthesis,
methanation, etc., this syngas is very acceptable.
[0014] Another important part of power recovery is to reduce the
energy losses of the waste-reforming kiln. Previously covered was a
process interface involving a conventional kiln, followed by a
desulfurizer and a high temperature filter in the CIP of patent
application Ser. No. 10/719,504 (examined by Ryan/Lewis) filed Nov.
21, 2003. The problem is that the kiln was operated at a high
temperature, followed by an even higher temperature steam/CO.sub.2
reformer which is then followed by the desulfurizer and high
temperature filter--all energy-inefficient from heat losses from
the process units themselves and from the complex of hot process
piping. Also this was expensive, as well.
[0015] Regarding Fischer-Tropsch, the challenge was to develop a
process train where the Fischer-Tropsch unit could produce enough
high carbon product, such as high density, unsaturated paraffin wax
containing little hydrogen, so that the carbon in the waste feed
would be sequestered in this product, without significant carbon
emissions leaving the process anywhere else. The Fischer-Tropsch
train also had to produce steam for a steam-turbo-generator to make
enough electricity to drive the process plant.
SUMMARY OF THE INVENTION
[0016] This invention relates to a power recovery process in waste
steam/CO.sub.2 reformers whereby a waste stream can be made to
release energy without having to burn the waste or the syngas and
consume oxygen and have large carbon dioxide emissions. This
invention does not make use of fuel cells as its critical component
but makes use of highly exothermic chemical reactors using syngas
to produce large amounts of heat, such as Fischer-Tropsch. It also
relates to control or elimination of the emissions of greenhouse
gases in the power recovery process of this invention with the goal
of producing energy in the future carbonless world economy.
[0017] The significant improvement in this process train for power
recovery is an improved duplex kiln that combines the functions of
the conventional kiln, steam/CO.sub.2 reformer, and the high
temperature filter into a single unit. The desulfurizer/getter bed
can operate at a lower temperature and can follow the duplex
kiln.
[0018] Further improvements that involve using the above duplex
kiln and getter bed in a process train that includes a heat
exchanger/steam superheater are disclosed that will rapidly
quench-cool the syngas down from 300 to 500.degree. C. (600 to
900.degree. F.) temperature range of the desulfurizer to
150.degree. C. (300.degree. F.). The concept here is to rapidly
quench the syngas so that the undesirable heavy hydrocarbon
recombination reactions (i.e. "De-Novo") that make dioxins and
furans do not have time to form, since they are kinetically
limited. These recombination reactions involve multi-step
polymerization &/or ring formation and are slowed as the
temperatures are lowered.
[0019] Next, the Brayton cycle turbine is used to recover energy
from the high temperature gas, while cooling it for feeding to both
the Fischer-Tropsch unit to produce the high-carbon content product
for sequestering the carbon and the shift converter and
pressure-swing absorber to produce hydrogen fuel.
[0020] As an alternative, a conventional indirectly fired,
calcining kiln can be used where the very hot syngas exiting from
the steam reformer can heat carbon dioxide gas or air to supply the
indirect heat to the kiln to take over from the natural gas burners
commonly used.
[0021] The Fischer-Tropsch reactor, as discussed above, is highly
exothermic and produces vast quantities of high quality steam for
operating a conventional steam turbo-generator system for powering
the plant.
[0022] So what has been accomplished in this invention is the
conversion of a waste stream by steam/CO.sub.2 reforming to produce
a syngas that is used in a Fischer-Tropsch reactor to produce
energy and sequester the carbon of the waste at the same time.
[0023] It will be obvious for those skilled in the art, to replace
the Fischer-Tropsch reactor with other highly exothermic reactors
that produce a high-carbon content product for sequestering carbon
and produce large amounts of energy. Also interchanging the syngas
cleaning process units around while keeping the same functionality
are covered under this invention. All such generalizations are
covered by this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] In FIG. 1, there is shown the improved duplex kiln that
combines the functions of the conventional kiln, steam/CO.sub.2
reformer, and the high temperature filter into a single unit. In
FIG. 2, is shown how the new concept of a duplex kiln can be
followed by a desulfurizer/getter bed, quench heat exchanger for
provided superheated steam for the duplex kiln, and the Brayton
turbine for generating power by cooling the syngas, which is then
fed to both a Fischer-Tropsch reactor and Shift/Pressure Swing
Absorption System. In FIG. 3 is shown the advantage of using a
Fischer-Tropsch process consisting only of two units that simply
makes the high-carbon product, makes steam and accomplishes
sequestration carbon balance in capturing nearly all of the carbon
dioxide emissions. FIG. 4 shows the spiral heat exchange
Fischer-Tropsch Reactor. In FIG. 5 is shown how the Fischer-Tropsch
process that makes paraffin wax product for carbon sequestration
accomplishes recycling the light hydrocarbons consisting of
methane, ethane, ethylene, propane, etc. to avoid their emissions
as powerful greenhouse gases (i.e. methane) and also recycling the
lighter hydrocarbons to help maintain a higher H.sub.2/CO ratio of
the syngas. It also describes how a waste stream can be made to
release energy without having to burn the waste or the syngas. At
the same time the waste can be converted into use carbon-containing
fertilizer, hydrogen fuel, and a carbon-sequestering, high-carbon
content product of important commercial value, such as unsaturated,
high-density paraffin wax.
[0025] FIG. 6 shows the use of a conventional indirectly fired,
calcining kiln where the very hot syngas exiting from the steam
reformer can heat carbon dioxide gas or air to supply the indirect
heat to the kiln to take over from the natural gas burners commonly
used. The process flowsheet layout is given in FIG. 7.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] In FIG. 1, the functionality of the preferred embodiment of
FIG. 1 is combined into a single kiln to increase the thermal
efficiency and reduce the cost. This design is referred to as the
Duplex Kiln. This new kiln concept combines all the high
temperature process components of the embodiment shown in FIG. 1
into a single unit, greatly reducing heat loss and thus achieving
very much higher thermal efficiency.
[0027] Referring to FIG. 1, the waste stream 100 is fed through a
sealed lockhopper 102 down into the internal region 103 of the kiln
104. The lockhopper is of novel design in that these two sliding
port rectangular knife gate valves are spaced apart so that the top
valve opens and a column of waste is dropped down through this
valve, at which point it is then closed, cutting through the column
of waste. Then the knife gate valve below is opened dropping the
portion of waste captured between these valves is dropped down into
the kiln. Next, the bottom valve is closed and the top valve
opened, thus repeating the cycling. What is novel is that these
sliding port rectangular knife gates have hardened sliding gate
edges driven by powerful hydraulic actuators that are capable of
cutting through a column of waste, such as municipal solid waste.
This is important since the column of waste will be produced by
intermittent loading from external sources and will be of varying
height depending on how quickly this waste is added to the column.
In this way a very intermittent waste stream is converted to a
steady stream of regular pulses of fixed amounts of waste are fed
into the kiln, making the kiln operation, for all practical
measures, a continuous process.
[0028] Referring to FIG. 1, once the waste 100 enters the kiln 104,
the hollow flight auger 106 moves this portion of waste admitted by
the knife gate lockhopper slowly along the kiln from left to right.
This waste is heated by very hot gas passing inside of these screw
auger flights 106. The outside of the kiln in this region is heated
by electrical heat tracing 108 to reduce heat loss. The kiln body
110 itself in this example is 48'' in diameter and 22 ft long with
the wall made of high temperature alloy, such as Incoloy 800H. The
waste is being steam/CO.sub.2 reformed in the region 103 of the
screw between these hollow flights 106 where the temperatures range
from around 200.degree. F. in the feed end at the left to around
900.degree. F. leaving the last screw flight on the right, at which
point the solids remaining after reforming drop out at the solids
exit, 112.
[0029] Referring to FIG. 1, after the syngas leaves the screw
flights moving to the right, they enter the annular regions 114 and
116 which are separated by a perforated heavy wall cylinder 118 of
Incoloy 800 HT which is heated inductively by the outside coils
120. This syngas moves to the right through this double annular
region where it is heated from 480-1050.degree. C. (900 to
1900.degree. F.). Within this annular region are located spiral
flights to swirl the gas in a gas cyclone operation for removal of
entrained solids. At its highest temperature this very hot syngas
passes through a porous alumina filter 122 on which any fine
particulate entrained material is deposited. As the solids build up
on this porous filter they can be removed by pulsing an external
steam source 124 entering through conduit 126 through rotary seal
128. As the solids deposited on this filter 122 are blown off, they
are moved to the left by spiral flights 130 to remove these fine
solids out the exit pipe 112. The syngas, which is now cleaned of
fines, passes through large ports 132 in the central shaft 134.
Inside this shaft there are swirl vanes 136 that thorough mix the
steam 124 added to this region with the syngas to complete the
reforming chemistry. This finished syngas passes through this swirl
vane region 138 from right to the left inside the central shaft
134. As this finished syngas leaves the swirl vane region it is
blocked by plug 140 at which point the finished syngas passes
through large ports 142 in the central to enter into the internal
region of the hollow flights 144. This very hot finished syngas at
about 1000.degree. C. (1800.degree. F.) is now rapidly cooled as it
gives up its sensible heat to the incoming solid waste 100 passing
countercurrently in the region 103 outside of these hollow flights
106. Once this finished syngas is cooled to about 150-480.degree.
C. (300-900.degree. F.) it passes from the internal volume of the
last hollow flight 146 through large ports 148 into the inside of
the chamber 150. This chamber 150 is fitted with a rotary seal 152
so the finished cooled syngas passes out of the kiln via conduit
154. The outer shell of the kiln 110 is egg-shaped in cross section
156 to allow ample regions for the syngas to pass outside the
hollow flights. This kiln shell is fitted with flanges 158 at both
ends that includes bearings 160 through which the internal central
shaft 134 rotates. There is a motor drive and gear assembly 162
that rotates the central shaft 134 around which are the hollow
flights 106, the annular heated cylinder 118 and its spiral flights
130.
[0030] Now referring to FIG. 2, the above kiln 104 is shown
interfaced to the shift/PSA unit using its exhaust recycle 236 and
the Fischer-Tropsch process 220 recycling the methane and light
hydrocarbon gases via 222 back to the steam/CO.sub.2 reforming
kiln. These streams involving the waste 100, the fuel cell anode
exhaust 210 and the Fischer-Tropsch overhead stream 222 are
combined with the proper amount of steam 224 to carryout the
steam/CO.sub.2 reforming inside the kiln 104. Particularly
important to note is that these two recycle steams both involve
greenhouse gases, CO.sub.2 and CH.sub.4, which would otherwise be
released to the atmosphere. For example, we find a long forgotten
reaction, that has not been commercially exploited, can be
accomplished. It is:
CH.sub.4+CO.sub.2.fwdarw.2H.sub.2+2CO
[0031] In our improved process these problem gases are not released
to environment but profitably utilized.
[0032] This reaction equilibrium favors the H.sub.2 and CO at
temperatures around or above 700.degree. C. (1300.degree. F.) so
that when the syngas moves from the hollow flight section of kiln
104 in FIG. 2 into the double annular regions 114, and 116, which
involves temperatures around 1050.degree. C. (1900.degree. F.), so
that this reaction is almost 100% completed as the synthesis gas
leaves kiln 104 in line 200. Note that this consumes CO.sub.2 and
produces more syngas that can be used in the fuel cell as well as
in Fischer-Tropsch. This reaction is favored at the high
temperatures of our steam/CO.sub.2 reformer wherein the syngas of
H.sub.2/CO ratio around 1.0 is produced. Also using our '465 patent
and its continuation, the reaction:
CH.sub.4+H.sub.2O.fwdarw.3H.sub.2+CO
can be accomplished in our steam/CO.sub.2 reformer to produce a
syngas of H.sub.2/CO=3, so again we can adjust the H.sub.2/CO ratio
to whatever Fischer-Tropsch needs (i.e. say 0.7 to 1.4). So
recycling this combination of CO.sub.2 and CH.sub.4 as well as
other light hydrocarbons is of significant advantage.
[0033] Here, using the empirical formula for typical municipal
solid waste, we show two reactions: first the conventional steam
reforming using a stoichiometric amount of steam to make just CO
and H.sub.2.
[0034] Referring to FIG. 2, the synthesis gas is moved by the
turbo-blower 210 powered by electric motor 212 and divided into
streams 214 and 216. Any excess heat from the Fischer-Tropsch
process 220 in the form of steam in line 224 can be used to drive a
conventional turbine 226 powering electric generator 228 for
providing electricity to operate the system as set forth in the
examples below.
Example #1
Stoichiometric Steam
[0035]
C.sub.1H.sub.1.67O.sub.0.47+0.53H.sub.2O.fwdarw.CO+1.36H.sub.2
[0036] In this case 1 kg of waste will yield 1.45 kg of syngas.
Example #2
Superstoichiometric in CO.sub.2 and C.sub.2H.sub.4
[0037] By contrast, here is the improved reforming reaction which
involves a substoichiometric amount of steam but has the light
hydrocarbon Fischer-Tropsch and shift/PSA overhead represented for
simplicity by C.sub.2H.sub.4, plus CO.sub.2 and H.sub.2, added.
C.sub.1H.sub.1.67O.sub.0.47+0.55C.sub.2H.sub.4+0.69H.sub.2+1.5CO.sub.2+0-
.04H.sub.2O.fwdarw.3.68CO+2.67H.sub.2 [1]
[0038] In this case, 1 kg of waste will yield 5.11 kg of syngas,
which is a very significant 350% increase in the mass of syngas
product formed from a given mass of waste.
[0039] This achieves the formation only of CO and H.sub.2, and thus
is stoichiometric which respect to the combination of steam plus
CO.sub.2 plus C.sub.2H.sub.4. Thus, less steam (i.e.
sub-stoichiometric) is required and greenhouse-problematic light
hydrocarbons and CO.sub.2 can be used in large amounts to achieve
overall the stoichiometric conversion to syngas desired with a
preferred H.sub.2/CO ratio around 0.73. CH.sub.4, C.sub.3H.sub.8 or
other light hydrocarbons are actually involved in the real world in
combination with C.sub.2H.sub.4 shown in the reaction. In a typical
Fischer-Tropsch process all of these light hydrocarbons are formed
and would be in the recycle. Thus, the use of Fischer-Tropsch is
simplified. The CH.sub.4 is produced as the major part of the waste
light gases coming off the tops of the Fischer-Tropsch gravity
separator. No distillation is required. Any other light gases that
are also carried along with the waste CH.sub.4 can go back to the
steam reformer as well.
[0040] We believe that it could even be economic to recycle 100% of
the CO.sub.2 and whatever optimum amount of CH.sub.4 from
Fischer-Tropsch to make the whole system balance, sequestering all
of the CO.sub.2 while making useful paraffin wax that is high in
carbon content, high in commercial value, and not burned in its
lifecycle. So in FIG. 2 the Improved Carbon Sequestration can be
accomplished as shown by the carbon balance. Thus, by adjusting the
carbon in the Shift/PSA recycle 236 plus the carbon in the
Fischer-Tropsch overhead recycle 222, the carbon in the waste 100
is made to just equal the carbon in the Fischer-Tropsch product. So
what could be accomplished is the total sequestration of the carbon
in the waste by the formation of the high carbon content paraffin
wax. It will be obvious to one skilled in the art to identify other
Fischer-Tropsch products passing through exit 221_that can be
selected that will accomplish this total carbon sequestration.
Commercially, there may be an economic optimum situation where one
may not want to sequester all of the carbon in the waste, but this
example shows that this is theoretically possible with our new
concept.
[0041] FIG. 3 shows how simplified the Fischer-Tropsch process can
become in this new steam/CO.sub.2 reforming process of waste
conversion with recycle streams. Referring to FIG. 3, the cleaned
and warm syngas 154 from the kiln 104 shown in FIG. 2 is passed
into an air cooler 300 where it is temperature-controlled to about
180.degree. C. (350.degree. F.) at the exit of the air cooler 301.
This stream 301 is then fed to the compressor 302 where the
pressure is increased from around one atmosphere (15 psig) to 3.5
MPa (468 psig) at its outlet 303 which feeds the Fischer-Tropsch
reactor 305 containing a Fischer-Tropsch catalyst 304 within its
vertical tubes 324. These vertical tubes containing catalyst are
surrounded with water 308 under pressure and this water boils to
maintain the proper temperature. The liquid paraffin formed as
desired is circulated by pump 312 at a rat controlled by valve 314.
This reactor carries out the synthesis reactions making a range of
hydrocarbons from CH.sub.4, light hydrocarbons up to heavy
hydrocarbon paraffins while releasing a very substantial amount of
heat.
[0042] The reaction below shows how the syngas produced in reaction
[1] above can be used to make high carbon-content products such as
high density, unsaturated paraffin wax as a means of sequestering
carbon in a product that has significant commercial value. The
other compounds formed can be recycled back into reaction [1] so
that they are not released to the environment. Also there are some
CO.sub.2, H.sub.2 and H.sub.2O that can be recycled as well from
the shift converter 230 and PSA unit 234, with the H.sub.2 stream
exiting in line 232. Again, C.sub.2H.sub.4 is being used to
represent the large range of light hydrocarbon gases for simplicity
of discussion.
3.68CO+2.67H.sub.2.fwdarw.0.055C.sub.20H.sub.30+0.55C.sub.2H.sub.4+1.47C-
O.sub.2+0.734H.sub.20 [2]
[0043] The temperature, pressure, H.sub.2/CO ratio of the syngas,
and the residence time together control the molecular range of the
Fischer-Tropsch products 316 that is then fed into the separator
318. The mixture of hydrocarbons gravimetrically separates here
into three fractions: water 320, paraffins 322 and light gases
overhead 332. So it can be seen that this is a very simple process,
not requiring complex distillation, crystallization, or boiling.
And it is this interfacing with the steam/CO.sub.2 reforming kiln
and the fuel cell that makes such a simplification possible and
novel.
[0044] It will be obvious to one skilled in the art to identify
other Fischer-Tropsch reactor concepts different from the
conventional catalyst--packed, multi-tube exothermic but isothermal
reactor. Such a reactor consists of a spiral heat exchanger where
the catalyst is placed in the spiral annular regions (made by
Alfa-Laval, particularly common in Europe). Such a design is shown
in FIG. 4 that shows the spiral heat exchange Fischer-Tropsch
Reactor wherein the syngas feed 500 enters into the spiral annuli
512 that are packed with supported catalyst. The converted syngas
consisting of the light gases and some unconverted syngas leaves
from nozzle 502. These annuli are immersed in water 508 with its
level controlled at the end of the annuli. The exothermic heat
boils the water to make steam in disengaging bell 506 which leaves
via 504 to feed a steam/turbo generator. The boiler feedwater
enters via nozzle 514. At the bottom of the reactor the liquid
paraffin wax forms within and drains out the exit of annuli at 518
leaves nozzle 516. Paraffin wax recycle from the separator 318
(shown in FIG. 3), enters the outer spiral annulus through nozzle
510.
[0045] Finally, FIG. 5 describes how a waste stream can be made to
release energy without having to burn the waste or the syngas. At
the same time the waste can be converted into use carbon-containing
fertilizer, hydrogen fuel, and a carbon-sequestering, high-carbon
content product of important commercial value, such as unsaturated,
high-density paraffin wax.
[0046] Referring to FIG. 5, the waste stream enters the process as
stream 100 into rotary kiln 450 where it is steam/CO.sub.2 reformed
via the chemistry in reaction [1] above to form a high-hydrogen
content syngas stream 154 where its high temperature heat is used
in boiler 416 to produce steam 418, as well as a high carbon
content product steam 112 that contains glass and metal as well as
a high NPK fertilizer solid particulate of commercial value. The
reaction in kiln 104 uses light gases, CO.sub.2, and steam recycled
as 402 from downstream process units consisting of shift converter
458, pressure-swing absorber 456, Fischer-Tropsch reactor 452 and
its paraffin product separator 454. This recycle stream 402 comes
from the combined streams 400 made up of 222 and 306 plus stream
414 made up of streams 410 and 412. The syngas 154 produced in kiln
104 is split into two streams 303 and 404, with 303 feeding the
Fischer-Tropsch units 452 and 454 producing paraffin product 322
and stream 404 feeding the Shift 458 and PSA 456 that produce
hydrogen product 408 and optional CO.sub.2 at 409. In addition, the
Fischer-Tropsch unit 452 is highly exothermic and produces large
amounts of steam 420 that can be used to drive a steam turbine to
make electricity to run the plant and be exported for sale. Water
streams 316 and 320 are used to make up boiler feedwater. So the
net result of this linkage and interface of the three process
blocks of steam-reforming of waste to the Shift/PSA and the
Fischer-Tropsch is to convert the waste to hydrogen fuel and into
high-carbon NPK fertilizer and carbon-sequestering paraffin with a
huge release of heat. And this is done without burning the waste
and without releasing the huge amounts of greenhouse gases typical
of a combustion process. This patent teaches the way of the future
of destroying waste and producing steam, heat and useful products
in the carbonless economy of the future.
[0047] FIG. 6 shows the use of a conventional indirectly fired,
calcining kiln where the very hot syngas exiting from the steam
reformer can heat carbon dioxide gas or air to supply the indirect
heat to the kiln to take over from the natural gas burners commonly
used. Now referring to FIG. 6, the above kiln 590 is shown
interfaced to the shift/PSA unit using its exhaust recycle 236 and
the Fischer-Tropsch process 220 recycling the methane and light
hydrocarbon gases via 222 back to the steam/CO.sub.2 reforming
kiln, and the products via 221. These streams involving the waste
100, the fuel cell anode exhaust 210 and the Fischer-Tropsch
overhead stream 222 are combined with the proper amount of steam in
line_224 to carryout the steam/CO.sub.2 reforming inside the kiln
104.
[0048] This reaction equilibrium favors the H.sub.2 and CO at
temperatures around or above 700.degree. C. (1300.degree. F.) so
that when the syngas moves from the conventional calcining kiln 104
in FIG. 6 into the steam/CO.sub.2 reformer, 600, which involves
temperatures around 1050.degree. C. (1900.degree. F.), so that this
reaction is almost 100% completed. Following this reactor, 600,
stream 205 passes into heat exchanger 206 wherein an inert gas,
such as CO.sub.2 produced elsewhere in the process, or outside air,
208 is heated by the very hot syngas in steam 205 to be fed via
streams 208 and 602 into a series of multiple indirect burners 608
of the conventional kiln. These burners, conventionally used for
natural gas, would be replaced with an injection jet that would
supply the very hot gas directly into the oven-furnace area of the
conventional kiln. The rest of the process is the same as in FIG.
2.
Example #3
CO.sub.7 Enriched Syngas
[0049] A further improvement in the reforming reaction which
involves a substoichiometric amount of steam but has the light
hydrocarbon Fischer-Tropsch and shift/PSA overhead represented for
simplicity by C.sub.2H.sub.4, plus CO.sub.2 and H.sub.2, added.
C.sub.1H.sub.1.67O.sub.0.47+0.2567C.sub.2H.sub.4+0.2CO.sub.2+1.434H.sub.-
2O.fwdarw.1.123CO+0.591CO.sub.2+3.029H.sub.2
[0050] In this case, the reformation reaction is allowed to form
CO.sub.2 in the syngas, such that the stoichiometric ratio of
(H.sub.2--CO.sub.2)/(CO+CO.sub.2)=1.42 which is favorable for the
Fischer-Tropsch reaction as follows:
1.123CO+0.591CO.sub.2+3.029H.sub.2.fwdarw.0.0757C.sub.20H.sub.30+0.2CO.s-
ub.2+1.904H.sub.2O
[0051] This achieves an increase in the amount of paraffin formed
and greenhouse-problematic light hydrocarbons and CO.sub.2 are
entirely recycle back into the reformer, with a small portion of
the water condensed as product water. Thus, the use of
Fischer-Tropsch is further simplified. As before, the CH.sub.4 is
produced as the major part of the waste light gases coming off the
tops of the Fischer-Tropsch gravity separator. No distillation is
required. Any other light gases that are also carried along with
the waste CH.sub.4 can go back to the steam reformer as well. The
important result is that there are no CO.sub.2 emissions since the
CO.sub.2 formation in the Fischer-Tropsch is entirely recycled back
into the reformer.
[0052] So in FIG. 2 what has been achieved in this case is the
entire elimination (i.e. stream 216 is zero) of the Shift/PSA
process step at a capital savings. Likewise, in FIG. 5, stream 404
is zero. So what is accomplished in this case is the total
sequestration of the carbon in the waste by the formation of the
high carbon content paraffin wax. It will be obvious to one skilled
in the art to identify other Fischer-Tropsch products that can be
selected that will accomplish this total carbon sequestration.
Commercially, there may be an economic optimum situation where one
may not want to sequester all of the carbon in the waste, but this
example shows that this is theoretically possible with our new
concept.
Example #4
Process Flowsheet Mass Balance
[0053] The process flowsheet layout based on FIG. 5, but with all
the process details, was completed and the mass balance done where
the flow split of sending syngas to Shift/PSA system and to
Fischer-Tropsch was varied. The chemistry within the steam reformer
was given in reaction [1] above and in the Fischer-Tropsch unit in
reaction [2] above. The results have been summarized in Table 2
below, showing how the products of the waste-to-energy plant, such
as hydrogen, water, carbon dioxide and paraffin can be varied
depending on the needs of the customer and the marketplace. The
case is for wet waste with 15% water and a scale of 4
tonnes/day.
TABLE-US-00002 TABLE 2 The Process Choices Set the Products That
Are Made Shift Fischer Net PSA Tropsch H.sub.2 H.sub.2 Water
CO.sub.2 Paraffin Electricity % % Recycle Kg/hr Kg/hr Kg/hr Kg/hr
kWe 62 38 Low 490 -1547 6587 859 185 62 38 Hi 395 -922 5823 1093
235 50 50 Hi 254 0 4096 1441 310 38 62 Hi 232 229 4416 1526 328 19
81 Hi 46 1475 2888 1984 426 0 100 Low 0 2264 1928 2290 492 0 100 Hi
0 3842 0 2875 618 0 100 OptCO.sub.2 0 1594 0 3851 861
[0054] As the process option is shifted more toward
Fischer-Tropsch, more paraffin, water, and electricity products are
made and less hydrogen fuel produced. With all Fischer-Tropsch, no
hydrogen and no carbon dioxide are produced and the amount of
water, paraffins, and electricity are maximized. The electricity is
a net number, after the internal electricity consumption within the
plant is removed and used. The last line in Table 2 covers the case
presented in Example #3, showing a great increase in
Fischer-Tropsch product as well as electricity generated.
Example #5
Process Flowsheet Heat & Mass Balance for Maximum Hydrogen
[0055] The process flowsheet layout is given in FIG. 7.
[0056] The detailed heat and mass balance for the Process flowsheet
for maximizing hydrogen production using a cellulose feed is given
below:
TABLE-US-00003 STREAM SUMMARY - Cellulose Stream Number 1 3 4
Stream Name Strm 1 Strm 3 Strm 4 Thermo Method Option GLOBAL GLOBAL
GLOBAL Vapor Fraction 0 1 0.2441006 Temperature C. 25 50 23.97223
Pressure kg/cm2 1.18822 18.30545 1.18822 Enthalpy kcal/hr
-568658.428 5939.92631 -562718.501 Entropy kcal/K/hr -1601.801
-55.70444 -1562.611 Vapor Density kg/m3 7.08434 0.5120275 Liquid 1
Density kg/m3 1145.39015 1145.55729 Liquid 1 Specific Gravity 60
F.@STP 1.14771 1.14767 Vapor Cp kcal/kgmo/C. 7.00204 6.96086 Vapor
Cv kcal/kgmo/C. 4.97593 4.97023 Liquid 1 Cp kcal/kgmo/C. 74.1567
73.88081 Vapor Viscosity cP 0.012585 0.0115689 Liquid 1 Viscosity
cP 1.35416 1.3574 Vapor Thermal Conductivity kcal/m/hr/C. 0.0869059
0.0769098 Liquid 1 Thermal Conductivity kcal/m/hr/C. 0.0433377
0.0434341 Vapor Flowrate m3v(NTP)/hr 382.50232 391.4952 Liquid 1
Flowrate m3l(NTP)/hr 0.6580313 0.6579975 Liquid 2 Flowrate
m3l(NTP)/hr 249.06799 247.15388 Molecular Weight 31.1575 10.6878
26.2756 Molar Flowrate kgmol/hr 54.4973 17.0678 71.5652 Mass
Flowrate kg/hr 1697.999625 182.4172328 1880.418569 Note: All Liquid
1 Phase calculations exclude Free Water Molar Flowrate By Component
200: D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr 2.20858
4.402E-15 2.20858 1245: SODIUM CHLORIDE kgmol/hr 0 0 0 62: WATER
kgmol/hr 52.2888 0.043561 52.3323 48: CARBON MONOXIDE kgmol/hr 0
5.66596 5.66596 1: HYDROGEN kgmol/hr 0 11.3563 11.3563 2: METHANE
kgmol/hr 0 0.002054 0.002054 49: CARBON DIOXIDE kgmol/hr 0 0 0 65:
ACETYLENE kgmol/hr 0 0 0 40: BENZENE kgmol/hr 0 0 0 3: ETHANE
kgmol/hr 0 1.442E-10 1.442E-10 4: PROPANE kgmol/hr 0 0 0 22:
ETHYLENE kgmol/hr 0 1.332E-09 1.332E-09 1088: PHENOL kgmol/hr 0 0 0
45: ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr 0 9.511E-16
9.511E-16 6: N-BUTANE kgmol/hr 0 0 0 5: I-BUTANE kgmol/hr 0 0 0 27:
I-BUTENE kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0 0 0 66: PROPYNE
kgmol/hr 0 1.797E-16 1.797E-16 3114: 2-BUTYNE kgmol/hr 0 1.76E-09
1.76E-09 Total kgmol/hr 54.4973 17.0678 71.5652 Molar Composition
By Component 200: D-Glucose molar % 0 0 0 201: Cellubiose molar %
4.05264114 2.57913E-14 3.086108891 1245: SODIUM CHLORIDE molar % 0
0 0 62: WATER molar % 95.94750566 0.255223286 73.12534584 48:
CARBON MONOXIDE molar % 0 33.1967799 7.91719998 1: HYDROGEN molar %
0 66.53640188 15.8684668 2: METHANE molar % 0 0.012034357
0.00287011 49: CARBON DIOXIDE molar % 0 0 0 65: ACETYLENE molar % 0
0 0 40: BENZENE molar % 0 0 0 3: ETHANE molar % 0 8.44866E-10
2.01495E-10 4: PROPANE molar % 0 0 0 22: ETHYLENE molar % 0
7.80417E-09 1.86124E-09 1088: PHENOL molar % 0 0 0 45: ETHYLBENZENE
molar % 0 0 0 23: PROPYLENE molar % 0 5.57248E-15 1.329E-15 6:
N-BUTANE molar % 0 0 0 5: I-BUTANE molar % 0 0 0 27: I-BUTENE molar
% 0 0 0 27: I-BUTENE molar % 0 0 0 66: PROPYNE molar % 0
1.05286E-15 2.511E-16 3114: 2-BUTYNE molar % 0 1.03118E-08
2.4593E-09 Total molar % 100 100 100 Stream Number 5 6 7 Stream
Name Strm 5 Strm 6 Strm 7 Thermo Method Option GLOBAL GLOBAL GLOBAL
Vapor Fraction 1 1 1 Temperature C. 500 500 500 Pressure kg/cm2
1.15309 1.15309 1.15309 Enthalpy kcal/hr 410945.746 433890.844
18334.3418 Entropy kcal/K/hr 929.212 1113.85 34.89752 Vapor Density
kg/m3 0.4624083 0.351273 6.12671 Liquid 1 Density kg/m3 Liquid 1
Specific Gravity 60 F.@STP Vapor Cp kcal/kgmo/C. 13.60159 10.36102
167.62174 Vapor Cv kcal/kgmo/C. 11.60822 8.37071 165.50288 Liquid 1
Cp kcal/kgmo/C. Vapor Viscosity cP 0.026881 0.0258333 0.0166158
Liquid 1 Viscosity cP Vapor Thermal Conductivity kcal/m/hr/C.
0.0914342 0.0974512 0.0383433 Liquid 1 Thermal Conductivity
kcal/m/hr/C. Vapor Flowrate m3v(NTP)/hr 1603.82705 2110.29555
7.07083 Liquid 1 Flowrate m3l(NTP)/hr Liquid 2 Flowrate m3l(NTP)/hr
Molecular Weight 26.2756 19.9695 342.3019 Molar Flowrate kgmol/hr
71.5652 94.1646 0.315511 Mass Flowrate kg/hr 1880.418569 1880.41998
108.0000148 Note: All Liquid 1 Phase calculations exclude Free
Water Molar Flowrate By Component 200: D-Glucose kgmol/hr 0 0 0
201: Cellubiose kgmol/hr 2.20858 0.445562 0.315511 1245: SODIUM
CHLORIDE kgmol/hr 0 0 0 62: WATER kgmol/hr 52.3323 42.2031 0 48:
CARBON MONOXIDE kgmol/hr 5.66596 2.08022 0 1: HYDROGEN kgmol/hr
11.3563 24.9749 0 2: METHANE kgmol/hr 0.002054 7.81226 0 49: CARBON
DIOXIDE kgmol/hr 0 16.5541 0 65: ACETYLENE kgmol/hr 0 5.637E-12 0
40: BENZENE kgmol/hr 0 5.338E-16 0 3: ETHANE kgmol/hr 1.442E-10
0.00007558 0 4: PROPANE kgmol/hr 0 0 0 22: ETHYLENE kgmol/hr
1.332E-09 5.602E-07 0 1088: PHENOL kgmol/hr 0 1.121E-15 0 45:
ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr 9.511E-16
2.044E-10 0 6: N-BUTANE kgmol/hr 0 7.099E-14 0 5: I-BUTANE kgmol/hr
0 4.108E-14 0 27: I-BUTENE kgmol/hr 0 1.714E-14 0 27: I-BUTENE
kgmol/hr 0 1.714E-14 0 66: PROPYNE kgmol/hr 1.797E-16 7.64E-15 0
3114: 2-BUTYNE kgmol/hr 1.76E-09 0.094368 0 Total kgmol/hr 71.5652
94.1646 0.315511 Molar Composition By Component 200: D-Glucose
molar % 0 0 0 201: Cellubiose molar % 3.086108891 0.473173571 100
1245: SODIUM CHLORIDE molar % 0 0 0 62: WATER molar % 73.12534584
44.81843495 0 48: CARBON MONOXIDE molar % 7.91719998 2.209131669 0
1: HYDROGEN molar % 15.8684668 26.52259979 0 2: METHANE molar %
0.00287011 8.29638739 0 49: CARBON DIOXIDE molar % 0 17.57996105 0
65: ACETYLENE molar % 0 5.98633E-12 0 40: BENZENE molar % 0
5.6688E-16 0 3: ETHANE molar % 2.01495E-10 8.02637E-05 0 4: PROPANE
molar % 0 0 0 22: ETHYLENE molar % 1.86124E-09 5.94916E-07 0 1088:
PHENOL molar % 0 1.19047E-15 0 45: ETHYLBENZENE molar % 0 0 0 23:
PROPYLENE molar % 1.329E-15 2.17067E-10 0 6: N-BUTANE molar % 0
7.53893E-14 0 5: I-BUTANE molar % 0 4.36257E-14 0 27: I-BUTENE
molar % 0 1.82022E-14 0 27: I-BUTENE molar % 0 1.82022E-14 0 66:
PROPYNE molar % 2.511E-16 8.11345E-15 0 3114: 2-BUTYNE molar %
2.4593E-09 0.100216005 0 Total molar % 100 100 100 Stream Number 8
9 10 Stream Name Strm 8 Strm 9 Strm 10 Thermo Method Option GLOBAL
CHANGED GLOBAL Vapor Fraction 1 1 1 Temperature C. 500 267
499.83311 Pressure kg/cm2 1.15309 1.03323 1.03323 Enthalpy kcal/hr
415533.433 121.05274 415654.486 Entropy kcal/K/hr 1075.271
0.1986506 1096.144 Vapor Density kg/m3 0.3322084 0.4077036
0.2977284 Liquid 1 Density kg/m3 Liquid 1 Specific Gravity 60
F.@STP Vapor Cp kcal/kgmo/C. 9.83285 8.59419 9.83058 Vapor Cv
kcal/kgmo/C. 7.84266 6.57159 7.84075 Liquid 1 Cp kcal/kgmo/C. Vapor
Viscosity cP 0.0253123 0.0189224 0.0253076 Liquid 1 Viscosity cP
Vapor Thermal Conductivity kcal/m/hr/C. 0.0985838 0.0343274
0.0985339 Liquid 1 Thermal Conductivity kcal/m/hr/C. Vapor Flowrate
m3v(NTP)/hr 2103.22472 1.24398 2104.4687 Liquid 1 Flowrate
m3l(NTP)/hr Liquid 2 Flowrate m3l(NTP)/hr Molecular Weight 18.8858
18.0153 18.8853 Molar Flowrate kgmol/hr 93.849 0.055508 93.9046
Mass Flowrate kg/hr 1772.413444 0.999993272 1773.416542 Note: All
Liquid 1 Phase calculations exclude Free Water Molar Flowrate By
Component 200: D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr
0.130051 0 0.130051 1245: SODIUM CHLORIDE kgmol/hr 0 0 0 62: WATER
kgmol/hr 42.2031 0.055508 42.2586 48: CARBON MONOXIDE kgmol/hr
2.08022 0 2.08022 1: HYDROGEN kgmol/hr 24.9749 0 24.9749 2: METHANE
kgmol/hr 7.81226 0 7.81226 49: CARBON DIOXIDE kgmol/hr 16.5541 0
16.5541 65: ACETYLENE kgmol/hr 5.637E-12 0 5.637E-12 40: BENZENE
kgmol/hr 5.338E-16 0 5.338E-16 3: ETHANE kgmol/hr 0.00007558 0
0.00007558 4: PROPANE kgmol/hr 0 0 0 22: ETHYLENE kgmol/hr
5.602E-07 0 5.602E-07 1088: PHENOL kgmol/hr 1.121E-15 0 1.121E-15
45: ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr 2.044E-10 0
2.044E-10 6: N-BUTANE kgmol/hr 7.099E-14 0 7.099E-14 5: I-BUTANE
kgmol/hr 4.108E-14 0 4.108E-14 27: I-BUTENE kgmol/hr 1.714E-14 0
1.714E-14 27: I-BUTENE kgmol/hr 1.714E-14 0 1.714E-14 66: PROPYNE
kgmol/hr 7.64E-15 0 7.64E-15 3114: 2-BUTYNE kgmol/hr 0 0.094368
Total kgmol/hr 93.849 0.055508 93.9046 Molar Composition By
Component 200: D-Glucose molar % 0 0 0 201: Cellubiose molar %
0.138574732 0 0.138492683 1245: SODIUM CHLORIDE molar % 0 0 0 62:
WATER molar % 44.96915257 100 45.00162931 48: CARBON MONOXIDE molar
% 2.216560645 0 2.215248241 1: HYDROGEN molar % 26.61179128 0
26.5960347 2: METHANE molar % 8.324286886 0 8.319358157 49: CARBON
DIOXIDE molar % 17.6390798 0 17.62863587 65: ACETYLENE molar %
6.00646E-12 0 6.0029E-12 40: BENZENE molar % 5.68786E-16 0
5.68449E-16 3: ETHANE molar % 8.05336E-05 0 8.04859E-05 4: PROPANE
molar % 0 0 0 22: ETHYLENE molar % 5.96916E-07 0 5.96563E-07 1088:
PHENOL molar % 1.19447E-15 0 1.19376E-15 45: ETHYLBENZENE molar % 0
0 0 23: PROPYLENE molar % 2.17797E-10 0 2.17668E-10 6: N-BUTANE
molar % 7.56428E-14 0 7.5598E-14 5: I-BUTANE molar % 4.37724E-14 0
4.37465E-14 27: I-BUTENE molar % 1.82634E-14 0 1.82526E-14 27:
I-BUTENE molar % 1.82634E-14 0 1.82526E-14 66: PROPYNE molar %
8.14074E-15 0 8.13592E-15 3114: 2-BUTYNE molar % 0 0.10049348 Total
molar % 100 100 100 Stream Number 11 12 14 Stream Name Strm 11 Strm
12 Strm 14 Thermo Method Option GLOBAL GLOBAL GLOBAL Vapor Fraction
1 1 0.6603743 Temperature C. 875 875 4.4 Pressure kg/cm2 0.9981011
0.9981011 0.894778 Enthalpy kcal/hr 784222.539 817911.152
-407395.817 Entropy kcal/K/hr 1489.791 1599.197 -1013.643 Vapor
Density kg/m3 0.193587 0.1609311 0.551586 Liquid 1 Density kg/m3
1037.15161 Liquid 1 Specific Gravity 60 F.@STP 0.9999917 Vapor Cp
kcal/kgmo/C. 11.06725 9.15389 7.20069 Vapor Cv kcal/kgmo/C. 9.07945
7.16653 5.2086
Liquid 1 Cp kcal/kgmo/C. Vapor Viscosity cP 0.0335965 0.032694
0.0119112 Liquid 1 Viscosity cP 1.54882 Vapor Thermal Conductivity
kcal/m/hr/C. 0.1559868 0.1819838 0.0642739 Liquid 1 Thermal
Conductivity kcal/m/hr/C. 0.4896245 Vapor Flowrate m3v(NTP)/hr
2104.4687 2531.34933 1671.63813 Liquid 1 Flowrate m3l(NTP)/hr
Liquid 2 Flowrate m3l(NTP)/hr 182.78458 Molecular Weight 18.8853
15.7005 15.7005 Molar Flowrate kgmol/hr 93.9046 112.9526 112.9526
Mass Flowrate kg/hr 1773.416542 1773.412296 1773.412296 Note: All
Liquid 1 Phase calculations exclude Free Water Molar Flowrate By
Component 200: D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr
0.130051 4.408E-15 4.408E-15 1245: SODIUM CHLORIDE kgmol/hr 0 0 0
62: WATER kgmol/hr 42.2586 39.0616 39.0616 48: CARBON MONOXIDE
kgmol/hr 2.08022 16.9496 16.9496 1: HYDROGEN kgmol/hr 24.9749
45.5062 45.5062 2: METHANE kgmol/hr 7.81226 0.002054 0.002054 49:
CARBON DIOXIDE kgmol/hr 16.5541 11.4332 11.4332 65: ACETYLENE
kgmol/hr 5.637E-12 1.176E-10 1.176E-10 40: BENZENE kgmol/hr
5.338E-16 0 0 3: ETHANE kgmol/hr 0.00007558 1.443E-10 1.443E-10 4:
PROPANE kgmol/hr 0 0 0 22: ETHYLENE kgmol/hr 5.602E-07 1.334E-09
1.334E-09 1088: PHENOL kgmol/hr 1.121E-15 0 0 45: ETHYLBENZENE
kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr 2.044E-10 9.52E-16 9.52E-16
6: N-BUTANE kgmol/hr 7.099E-14 0 0 5: I-BUTANE kgmol/hr 4.108E-14 0
0 27: I-BUTENE kgmol/hr 1.714E-14 0 0 27: I-BUTENE kgmol/hr
1.714E-14 0 0 66: PROPYNE kgmol/hr 7.64E-15 1.798E-16 1.798E-16
3114: 2-BUTYNE kgmol/hr 1.761E-09 1.761E-09 Total kgmol/hr 93.9046
112.953 112.953 Molar Composition By Component 200: D-Glucose molar
% 0 0 0 201: Cellubiose molar % 0.138492683 3.90251E-15 3.90251E-15
1245: SODIUM CHLORIDE molar % 0 0 0 62: WATER molar % 45.00162931
34.58217135 34.58217135 48: CARBON MONOXIDE molar % 2.215248241
15.0058874 15.0058874 1: HYDROGEN molar % 26.5960347 40.28773029
40.28773029 2: METHANE molar % 8.319358157 0.001818455 0.001818455
49: CARBON DIOXIDE molar % 17.62863587 10.12208618 10.12208618 65:
ACETYLENE molar % 6.0029E-12 1.04114E-10 1.04114E-10 40: BENZENE
molar % 5.68449E-16 0 0 3: ETHANE molar % 8.04859E-05 1.27752E-10
1.27752E-10 4: PROPANE molar % 0 0 0 22: ETHYLENE molar %
5.96563E-07 1.18102E-09 1.18102E-09 1088: PHENOL molar %
1.19376E-15 0 0 45: ETHYLBENZENE molar % 0 0 0 23: PROPYLENE molar
% 2.17668E-10 8.42828E-16 8.42828E-16 6: N-BUTANE molar %
7.5598E-14 0 0 5: I-BUTANE molar % 4.37465E-14 0 0 27: I-BUTENE
molar % 1.82526E-14 0 0 27: I-BUTENE molar % 1.82526E-14 0 0 66:
PROPYNE molar % 8.13592E-15 1.59181E-16 1.59181E-16 3114: 2-BUTYNE
molar % 1.55906E-09 1.55906E-09 Total molar % 100 100 100 Stream
Number 15 16 17 Stream Name Strm 15 Strm 16 Strm 17 Thermo Method
Option GLOBAL CHANGED GLOBAL Vapor Fraction 1 0 1 Temperature C.
3.8523 3.8523 3.8523 Pressure kg/cm2 0.7914549 0.7914549 0.7914549
Enthalpy kcal/hr 2003.49464 -409399.315 2003.49464 Entropy
kcal/K/hr 191.0706 -1186.391 191.0706 Vapor Density kg/m3 0.4889622
0.4889622 Liquid 1 Density kg/m3 1037.60562 Liquid 1 Specific
Gravity 60 F.@STP Vapor Cp kcal/kgmo/C. 7.1993 7.1993 Vapor Cv
kcal/kgmo/C. 5.20779 5.20779 Liquid 1 Cp kcal/kgmo/C. 18.09128
Vapor Viscosity cP 0.0118909 0.0118909 Liquid 1 Viscosity cP
1.57615 Vapor Thermal Conductivity kcal/m/hr/C. 0.0640952 0.0640952
Liquid 1 Thermal Conductivity kcal/m/hr/C. 0.4887219 Vapor Flowrate
m3v(NTP)/hr 1673.04691 1673.04691 Liquid 1 Flowrate m3l(NTP)/hr
Liquid 2 Flowrate m3l(NTP)/hr 182.47997 Molecular Weight 14.5114
18.0184 14.5114 Molar Flowrate kgmol/hr 74.6539 38.2987 74.6539
Mass Flowrate kg/hr 1083.332604 690.0812961 1083.332604 Note: All
Liquid 1 Phase calculations exclude Free Water Molar Flowrate By
Component 200: D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr
4.408E-15 1.431E-20 4.408E-15 1245: SODIUM CHLORIDE kgmol/hr 0 0 0
62: WATER kgmol/hr 0.76774 38.2936 0.76774 48: CARBON MONOXIDE
kgmol/hr 16.9495 0.000132 16.9495 1: HYDROGEN kgmol/hr 45.5061
0.000297 45.5061 2: METHANE kgmol/hr 0.002054 2.301E-08 0.002054
49: CARBON DIOXIDE kgmol/hr 11.4285 0.004673 11.4285 65: ACETYLENE
kgmol/hr 1.176E-10 3.819E-16 0 40: BENZENE kgmol/hr 0 0 0 3: ETHANE
kgmol/hr 1.443E-10 2.064E-15 1.443E-10 4: PROPANE kgmol/hr 0 0 0
22: ETHYLENE kgmol/hr 1.334E-09 5.218E-14 1.334E-09 1088: PHENOL
kgmol/hr 0 0 0 45: ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE
kgmol/hr 9.519E-16 6.283E-20 9.519E-16 6: N-BUTANE kgmol/hr 0 0 0
5: I-BUTANE kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0 0 0 27: I-BUTENE
kgmol/hr 0 0 0 66: PROPYNE kgmol/hr 1.798E-16 0 1.798E-16 3114:
2-BUTYNE kgmol/hr 1.761E-09 5.718E-15 1.761E-09 Total kgmol/hr
74.6539 38.2987 74.6539 Molar Composition By Component 200:
D-Glucose molar % 0 0 0 201: Cellubiose molar % 5.90458E-15
3.73642E-20 5.90458E-15 1245: SODIUM CHLORIDE molar % 0 0 0 62:
WATER molar % 1.028399052 99.98668362 1.028399052 48: CARBON
MONOXIDE molar % 22.70410521 0.000344659 22.70410521 1: HYDROGEN
molar % 60.95609205 0.000775483 60.95609205 2: METHANE molar %
0.002751363 6.00804E-08 0.002751363 49: CARBON DIOXIDE molar %
15.30864429 0.012201459 15.30864429 65: ACETYLENE molar %
1.57527E-10 9.97162E-16 0 40: BENZENE molar % 0 0 0 3: ETHANE molar
% 1.93292E-10 5.38922E-15 1.93292E-10 4: PROPANE molar % 0 0 0 22:
ETHYLENE molar % 1.78691E-09 1.36245E-13 1.78691E-09 1088: PHENOL
molar % 0 0 0 45: ETHYLBENZENE molar % 0 0 0 23: PROPYLENE molar %
1.27508E-15 1.64053E-19 1.27508E-15 6: N-BUTANE molar % 0 0 0 5:
I-BUTANE molar % 0 0 0 27: I-BUTENE molar % 0 0 0 27: I-BUTENE
molar % 0 0 0 66: PROPYNE molar % 2.40845E-16 0 2.40845E-16 3114:
2-BUTYNE molar % 2.35889E-09 1.493E-14 2.35889E-09 Total molar %
100 100 100 Stream Number 19 20 21 Stream Name Strm 19 Strm 20 Strm
21 Thermo Method Option GLOBAL GLOBAL CHANGED Vapor Fraction 1 1 1
Temperature C. 635.45059 260 260 Pressure kg/cm2 21.09209 21.08505
21.09209 Enthalpy kcal/hr 366570.079 144383.986 57054.8364 Entropy
kcal/K/hr 380.4712 65.87408 -92.54735 Vapor Density kg/m3 3.95258
6.72517 9.07162 Liquid 1 Density kg/m3 Liquid 1 Specific Gravity 60
F.@STP Vapor Cp kcal/kgmo/C. 8.17398 7.68643 10.81732 Vapor Cv
kcal/kgmo/C. 6.18082 5.67534 7.68247 Liquid 1 Cp kcal/kgmo/C. Vapor
Viscosity cP 0.0314229 0.0197539 0.0183392 Liquid 1 Viscosity cP
Vapor Thermal Conductivity kcal/m/hr/C. 0.1824967 0.1109855
0.0380113 Liquid 1 Thermal Conductivity kcal/m/hr/C. Vapor Flowrate
m3v(NTP)/hr 1673.04691 1673.04691 702.22658 Liquid 1 Flowrate
m3l(NTP)/hr Liquid 2 Flowrate m3l(NTP)/hr Molecular Weight 14.5114
14.5114 18.0153 Molar Flowrate kgmol/hr 74.6539 74.6539 31.3344
Mass Flowrate kg/hr 1083.332604 1083.332604 564.4986163 Note: All
Liquid 1 Phase calculations exclude Free Water Molar Flowrate By
Component 200: D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr
4.408E-15 4.408E-15 0 1245: SODIUM CHLORIDE kgmol/hr 0 0 0 62:
WATER kgmol/hr 0.76774 0.76774 31.3344 48: CARBON MONOXIDE kgmol/hr
16.9495 16.9495 0 1: HYDROGEN kgmol/hr 45.5061 45.5061 0 2: METHANE
kgmol/hr 0.002054 0.002054 0 49: CARBON DIOXIDE kgmol/hr 11.4285
11.4285 0 65: ACETYLENE kgmol/hr 0 0 0 40: BENZENE kgmol/hr 0 0 0
3: ETHANE kgmol/hr 1.443E-10 1.443E-10 0 4: PROPANE kgmol/hr 0 0 0
22: ETHYLENE kgmol/hr 1.334E-09 1.334E-09 0 1088: PHENOL kgmol/hr 0
0 0 45: ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr
9.519E-16 9.519E-16 0 6: N-BUTANE kgmol/hr 0 0 0 5: I-BUTANE
kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0
0 0 66: PROPYNE kgmol/hr 1.798E-16 1.798E-16 0 3114: 2-BUTYNE
kgmol/hr 1.761E-09 1.761E-09 0 Total kgmol/hr 74.6539 74.6539
31.3344 Molar Composition By Component 200: D-Glucose molar % 0 0 0
201: Cellubiose molar % 5.90458E-15 5.90458E-15 0 1245: SODIUM
CHLORIDE molar % 0 0 0 62: WATER molar % 1.028399052 1.028399052
100 48: CARBON MONOXIDE molar % 22.70410521 22.70410521 0 1:
HYDROGEN molar % 60.95609205 60.95609205 0 2: METHANE molar %
0.002751363 0.002751363 0 49: CARBON DIOXIDE molar % 15.30864429
15.30864429 0 65: ACETYLENE molar % 0 0 0 40: BENZENE molar % 0 0 0
3: ETHANE molar % 1.93292E-10 1.93292E-10 0 4: PROPANE molar % 0 0
0 22: ETHYLENE molar % 1.78691E-09 1.78691E-09 0 1088: PHENOL molar
% 0 0 0 45: ETHYLBENZENE molar % 0 0 0 23: PROPYLENE molar %
1.27508E-15 1.27508E-15 0 6: N-BUTANE molar % 0 0 0 5: I-BUTANE
molar % 0 0 0 27: I-BUTENE molar % 0 0 0 27: I-BUTENE molar % 0 0 0
66: PROPYNE molar % 2.40845E-16 2.40845E-16 0 3114: 2-BUTYNE molar
% 2.35889E-09 2.35889E-09 0 Total molar % 100 100 100 Stream Number
22 23 24 Stream Name Strm 22 Strm 23 Strm 24 Thermo Method Option
GLOBAL GLOBAL GLOBAL Vapor Fraction 1 1 0.8030047 Temperature C.
256.87599 375.08737 4.4 Pressure kg/cm2 21.08505 18.62596 18.47098
Enthalpy kcal/hr 201438.822 312069.389 -220645.816 Entropy
kcal/K/hr 155.5943 348.3435 -990.4445 Vapor Density kg/m3 7.32523
5.26004 11.74154 Liquid 1 Density kg/m3 1040.04221 Liquid 1
Specific Gravity 60 F.@STP 0.9973416 Vapor Cp kcal/kgmo/C. 8.16233
8.50312 7.5658 Vapor Cv kcal/kgmo/C. 6.08656 6.48094 5.45328 Liquid
1 Cp kcal/kgmo/C. Vapor Viscosity cP 0.018348 0.0209351 0.0117894
Liquid 1 Viscosity cP 1.54603 Vapor Thermal Conductivity
kcal/m/hr/C. 0.085113 0.1137605 0.0701938 Liquid 1 Thermal
Conductivity kcal/m/hr/C. 0.4903894 Vapor Flowrate m3v(NTP)/hr
2375.27349 2375.27349 1907.35568 Liquid 1 Flowrate m3l(NTP)/hr
Liquid 2 Flowrate m3l(NTP)/hr 100.38398 Molecular Weight 15.5473
15.5473 15.5473 Molar Flowrate kgmol/hr 105.9883 105.9883 105.9883
Mass Flowrate kg/hr 1647.831897 1647.831897 1647.831897 Note: All
Liquid 1 Phase calculations exclude Free Water Molar Flowrate By
Component 200: D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr
4.408E-15 4.408E-15 4.408E-15 1245: SODIUM CHLORIDE kgmol/hr 0 0 0
62: WATER kgmol/hr 32.1021 20.821 20.8209 48: CARBON MONOXIDE
kgmol/hr 16.9495 5.66831 5.66831 1: HYDROGEN kgmol/hr 45.5061
56.7872 56.7872 2: METHANE kgmol/hr 0.002054 0.002054 0.002054
49: CARBON DIOXIDE kgmol/hr 11.4285 22.7097 22.7097 65: ACETYLENE
kgmol/hr 0 0 0 40: BENZENE kgmol/hr 0 0 0 3: ETHANE kgmol/hr
1.443E-10 1.443E-10 1.443E-10 4: PROPANE kgmol/hr 0 0 0 22:
ETHYLENE kgmol/hr 1.334E-09 1.334E-09 1.334E-09 1088: PHENOL
kgmol/hr 0 0 0 45: ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE
kgmol/hr 9.519E-16 9.519E-16 9.519E-16 6: N-BUTANE kgmol/hr 0 0 0
5: I-BUTANE kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0 0 0 27: I-BUTENE
kgmol/hr 0 0 0 66: PROPYNE kgmol/hr 1.798E-16 1.798E-16 1.798E-16
3114: 2-BUTYNE kgmol/hr 1.761E-09 1.761E-09 1.761E-09 Total
kgmol/hr 105.988 105.988 105.988 Molar Composition By Component
200: D-Glucose molar % 0 0 0 201: Cellubiose molar % 4.15896E-15
4.15896E-15 4.15896E-15 1245: SODIUM CHLORIDE molar % 0 0 0 62:
WATER molar % 30.28842888 19.64467676 19.64458241 48: CARBON
MONOXIDE molar % 15.99190474 5.348067706 5.348067706 1: HYDROGEN
molar % 42.9351436 53.57889572 53.57889572 2: METHANE molar %
0.001937955 0.001937955 0.001937955 49: CARBON DIOXIDE molar %
10.78282447 21.42667094 21.42667094 65: ACETYLENE molar % 0 0 0 40:
BENZENE molar % 0 0 0 3: ETHANE molar % 1.36147E-10 1.36147E-10
1.36147E-10 4: PROPANE molar % 0 0 0 22: ETHYLENE molar %
1.25863E-09 1.25863E-09 1.25863E-09 1088: PHENOL molar % 0 0 0 45:
ETHYLBENZENE molar % 0 0 0 23: PROPYLENE molar % 8.98121E-16
8.98121E-16 8.98121E-16 6: N-BUTANE molar % 0 0 0 5: I-BUTANE molar
% 0 0 0 27: I-BUTENE molar % 0 0 0 27: I-BUTENE molar % 0 0 0 66:
PROPYNE molar % 1.69642E-16 1.69642E-16 1.69642E-16 3114: 2-BUTYNE
molar % 1.66151E-09 1.66151E-09 1.66151E-09 Total molar % 100 100
100 Stream Number 25 26 27 Stream Name Strm 25 Strm 26 Strm 27
Thermo Method Option CHANGED GLOBAL GLOBAL Vapor Fraction 0 1 1
Temperature C. 4.39847 4.39847 4.39847 Pressure kg/cm2 18.46043
18.46043 18.46043 Enthalpy kcal/hr -221779.766 1134.09787
1651.37154 Entropy kcal/K/hr -643.5034 -346.8443 -255.336 Vapor
Density kg/m3 11.7349 1.56295 Liquid 1 Density kg/m3 1040.04201
Liquid 1 Specific Gravity 60 F.@STP Vapor Cp kcal/kgmo/C. 7.56569
6.92733 Vapor Cv kcal/kgmo/C. 5.45325 4.9238 Liquid 1 Cp
kcal/kgmo/C. 18.04647 Vapor Viscosity cP 0.0117892 0.0086131 Liquid
1 Viscosity cP 1.54611 Vapor Thermal Conductivity kcal/m/hr/C.
0.0701924 0.1437823 Liquid 1 Thermal Conductivity kcal/m/hr/C.
0.4903864 Vapor Flowrate m3v(NTP)/hr 1907.35804 1018.04118 Liquid 1
Flowrate m3l(NTP)/hr Liquid 2 Flowrate m3l(NTP)/hr 100.383
Molecular Weight 18.1334 14.9129 2.0159 Molar Flowrate kgmol/hr
20.8791 85.1092 45.4265 Mass Flowrate kg/hr 378.6090719 1269.224989
91.57528135 Note: All Liquid 1 Phase calculations exclude Free
Water Molar Flowrate By Component 200: D-Glucose kgmol/hr 0 0 0
201: Cellubiose kgmol/hr 1.596E-19 4.408E-15 0 1245: SODIUM
CHLORIDE kgmol/hr 0 0 0 62: WATER kgmol/hr 20.7773 0.043565 0 48:
CARBON MONOXIDE kgmol/hr 0.00048 5.66783 0 1: HYDROGEN kgmol/hr
0.004106 56.7832 45.4265 2: METHANE kgmol/hr 2.447E-07 0.002054 0
49: CARBON DIOXIDE kgmol/hr 0.09716 22.6126 0 65: ACETYLENE
kgmol/hr 0 0 0 40: BENZENE kgmol/hr 0 0 0 3: ETHANE kgmol/hr
2.097E-14 1.442E-10 0 4: PROPANE kgmol/hr 0 0 0 22: ETHYLENE
kgmol/hr 5.284E-13 1.333E-09 0 1088: PHENOL kgmol/hr 0 0 0 45:
ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr 4.697E-19
9.515E-16 0 6: N-BUTANE kgmol/hr 0 0 0 5: I-BUTANE kgmol/hr 0 0 0
27: I-BUTENE kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0 0 0 66: PROPYNE
kgmol/hr 0 1.797E-16 0 3114: 2-BUTYNE kgmol/hr 6.377E-14 1.761E-09
0 Total kgmol/hr 20.8791 85.1092 45.4265 Molar Composition By
Component 200: D-Glucose molar % 0 0 0 201: Cellubiose molar %
7.64401E-19 5.17923E-15 0 1245: SODIUM CHLORIDE molar % 0 0 0 62:
WATER molar % 99.51243109 0.051187181 0 48: CARBON MONOXIDE molar %
0.00229895 6.659479821 0 1: HYDROGEN molar % 0.019665599
66.71805163 100 2: METHANE molar % 1.17199E-06 0.00241337 0 49:
CARBON DIOXIDE molar % 0.465345729 26.56892557 0 65: ACETYLENE
molar % 0 0 0 40: BENZENE molar % 0 0 0 3: ETHANE molar %
1.00435E-13 1.69429E-10 0 4: PROPANE molar % 0 0 0 22: ETHYLENE
molar % 2.53076E-12 1.56622E-09 0 1088: PHENOL molar % 0 0 0 45:
ETHYLBENZENE molar % 0 0 0 23: PROPYLENE molar % 2.24962E-18
1.11798E-15 0 6: N-BUTANE molar % 0 0 0 5: I-BUTANE molar % 0 0 0
27: I-BUTENE molar % 0 0 0 27: I-BUTENE molar % 0 0 0 66: PROPYNE
molar % 0 2.11141E-16 0 3114: 2-BUTYNE molar % 3.05425E-13
2.06911E-09 0 Total molar % 100 100 100 Stream Number 28 29 30
Stream Name Strm 28 Strm 29 Strm 30 Thermo Method Option GLOBAL
GLOBAL GLOBAL Vapor Fraction 0.9994618 1 0.9979077 Temperature C.
4.39847 4.39847 4.39847 Pressure kg/cm2 18.46043 18.46043 18.46043
Enthalpy kcal/hr -2251.94686 -4036.65963 114.87892 Entropy
kcal/K/hr -156.1731 -138.7223 -75.53467 Vapor Density kg/m3
24.30074 39.15895 8.31097 Liquid 1 Density kg/m3 1043.39783
1036.9372 Liquid 1 Specific Gravity 60 F.@STP 0.9949659 0.9997428
Vapor Cp kcal/kgmo/C. 8.5313 10.31671 6.99413 Vapor Cv kcal/kgmo/C.
6.12765 7.1849 4.95039 Liquid 1 Cp kcal/kgmo/C. Vapor Viscosity cP
0.0150956 0.0144267 0.0112137 Liquid 1 Viscosity cP 1.54611 1.54611
Vapor Thermal Conductivity kcal/m/hr/C. 0.0353254 0.0165414
0.0772689 Liquid 1 Thermal Conductivity kcal/m/hr/C. 0.4903864
0.4903864 Vapor Flowrate m3v(NTP)/hr 888.83821 506.76397 381.75248
Liquid 1 Flowrate m3l(NTP)/hr Liquid 2 Flowrate m3l(NTP)/hr
0.1036698 0.1701677 Molecular Weight 29.6766 44.0099 10.6895 Molar
Flowrate kgmol/hr 39.6827 22.6126 17.0701 Mass Flowrate kg/hr
1177.647615 995.1782647 182.470834 Note: All Liquid 1 Phase
calculations exclude Free Water Molar Flowrate By Component 200:
D-Glucose kgmol/hr 0 0 0 201: Cellubiose kgmol/hr 4.408E-15 0
4.408E-15 1245: SODIUM CHLORIDE kgmol/hr 0 0 0 62: WATER kgmol/hr
0.043565 0 0.043565 48: CARBON MONOXIDE kgmol/hr 5.66783 0 5.66783
1: HYDROGEN kgmol/hr 11.3566 0 11.3566 2: METHANE kgmol/hr 0.002054
0 0.002054 49: CARBON DIOXIDE kgmol/hr 22.6126 22.6126 0 65:
ACETYLENE kgmol/hr 0 0 0 40: BENZENE kgmol/hr 0 0 0 3: ETHANE
kgmol/hr 1.442E-10 0 1.442E-10 4: PROPANE kgmol/hr 0 0 0 22:
ETHYLENE kgmol/hr 1.333E-09 0 1.333E-09 1088: PHENOL kgmol/hr 0 0 0
45: ETHYLBENZENE kgmol/hr 0 0 0 23: PROPYLENE kgmol/hr 9.515E-16 0
9.515E-16 6: N-BUTANE kgmol/hr 0 0 0 5: I-BUTANE kgmol/hr 0 0 0 27:
I-BUTENE kgmol/hr 0 0 0 27: I-BUTENE kgmol/hr 0 0 0 66: PROPYNE
kgmol/hr 1.797E-16 0 1.797E-16 3114: 2-BUTYNE kgmol/hr 1.761E-09 0
1.761E-09 Total kgmol/hr 39.6827 22.6126 17.0701 Molar Composition
By Component 200: D-Glucose molar % 0 0 0 201: Cellubiose molar %
1.11081E-14 0 2.58229E-14 1245: SODIUM CHLORIDE molar % 0 0 0 62:
WATER molar % 0.109783356 0 0.25521233 48: CARBON MONOXIDE molar %
14.2828739 0 33.20326184 1: HYDROGEN molar % 28.61851638 0
66.52919432 2: METHANE molar % 0.005176059 0 0.012032736 49: CARBON
DIOXIDE molar % 56.98352179 100 0 65: ACETYLENE molar % 0 0 0 40:
BENZENE molar % 0 0 0 3: ETHANE molar % 3.63383E-10 0 8.44752E-10
4: PROPANE molar % 0 0 0 22: ETHYLENE molar % 3.35915E-09 0
7.80898E-09 1088: PHENOL molar % 0 0 0 45: ETHYLBENZENE molar % 0 0
0 23: PROPYLENE molar % 2.39777E-15 0 5.57407E-15 6: N-BUTANE molar
% 0 0 0 5: I-BUTANE molar % 0 0 0 27: I-BUTENE molar % 0 0 0 27:
I-BUTENE molar % 0 0 0 66: PROPYNE molar % 4.52842E-16 0
1.05272E-15 3114: 2-BUTYNE molar % 4.4377E-09 0 1.03163E-08 Total
molar % 100 100 100
[0057] The purpose of this optimization was to maximize the
hydrogen production, minimize the need for electric grid power to
operate the plant, and produce dry ice (liquid carbonic) product.
The feedstock in this example is the dimer of cellulose, called
cellubiose. This dimer portion of the large cellulose chain is
replicated some 25,000 to 250,000 times.
[0058] The biomass enters the rotary kiln steam reformer as a solid
and/or liquid phase together with the recycle gases. Within the
kiln this mixture is heated, volatiles are vaporized, solids are
chemically broken and decomposed, and the mixture is further heated
as it moves from left to right through the kiln. At the end of the
kiln, solids are removed. These solids are about 15% (by mass) of
the biomass feed. With an agricultural or forest biomass feedstock,
this solid product stream is a valuable freely-flowing,
gravel-like, slow-release form of phosphorus/potassium fertilizer.
The gases generated inside the kiln react with the water that
enters with the biomass and with any additional water that comes
with the recycle stream. The steam/carbon dioxide reforming
chemical reaction is endothermic (it requires supplying energy) and
occurs as the key step in the process generating a syngas stream
consisting of hydrogen, carbon monoxide, carbon dioxide, water and
other light gases, such as methane, ethane, ethylene, etc.
[0059] The hot syngas leaving the rotary kiln is heated, mixed with
hot superheated steam, and enters the vertical steam reformer where
it is further heated to complete the steam/carbon dioxide reforming
reaction producing the highest concentration of hydrogen with the
least amount of other organic contaminants, such as higher
hydrocarbons and aromatics.
[0060] Intellergy's system addresses biomass phase-change as a
solid-to-vapor chemical decomposition. The biomass is decomposed
into a vapor by breaking the chemical bonds. This process is not
the classical solid-to-liquid transition (heat of melting), or the
liquid-to-vapor transition (heat of vaporization).
[0061] As these molecular fragments move through the kiln, the
temperature increases, causing further decomposition by the
hydroxyl radical attacking and breaking the next stronger bond,
such as carbon-carbon bonds. The last and toughest bonds to be
attacked are the aromatic carbon-carbon bonds. This decomposition
results in the aromatic ring coming apart which creates other
organic gases such as ethane, ethylene and butyne. Small amounts of
these gases can recombine to form other very stable aromatic
compounds.
[0062] This very hot syngas leaving the steam reformer passes
through heat exchangers to recover energy to supply heat to
processing equipment or to generate steam for process use and/or
power generation. The cool hydrogen-rich syngas is passed to the
hydrogen purification section, shown in the on the right-hand
portion of the graphic in FIG. 2, where the carbon monoxide is
reacted with more superheated steam to form carbon dioxide and
additional hydrogen as well as release of heat. This rich hydrogen
gas mixture is purified in a commercial pressure swing adsorption
unit yielding a high purity hydrogen stream ranging from 99.9% to
99.99% purity. The remaining carbon dioxide and other light gases
pass overhead into the carbon dioxide recovery system. Here a clean
carbon dioxide stream is produced that feeds a commercial carbon
dioxide liquefaction plant where either liquid carbon dioxide
(liquid carbonic) or dry ice is produced. The remaining light gases
are recycled to the kiln.
[0063] Referring to FIG. 7 the simulation modules M-1, H-2, H-20,
S-4, and R-3 model the commercial rotary kiln. M-1 mixes the feed
biomass with the recycle gases adiabatically. The H-20 module
preheats the recycle gas while the H-2 module adds enough heat to
the material leaving M-1 to change its phase to a vapor and heat it
to 400 to 500.degree. C. Module S-4 removes the freely-flowing
granular residue, 15% of the biomass on a dry basis, which is
formed in the rotary kiln. This residue is high in carbon content.
R-3 calculates the equilibrium vapor composition using Gibbs Free
Energy minimization isothermally at 400 to 500.degree. C. The heat
added to the commercial kiln is supplied by recovered process heat
and trimmed with electric heat to control the reaction temperature
at 400.degree. to 500.degree. C.
[0064] Simulation modules M-5, H-6, and R-7 model the commercial
steam reformer. M-5 mixes the product from the rotary kiln at 1
atmosphere with superheated steam added at 300 PSIA and 267.degree.
C. Module H-6 heats the steam reformer feed to around 875.degree.
C. The steam reformer, R-7, is modeled as an isothermal reactor.
The heat added to the commercial steam reformer is supplied by
recovered process heat and trimmed with electric heat to control
the reaction temperature at around 875.degree. C.
[0065] Module X-8 models a commercial heat exchanger cooling the
steam reformer effluent while recovering energy to be returned to
the process. Water is condensed and removed in module F-9 which
models a commercial vapor liquid separator. The vapor leaving F-9
flows through module S-10, a commercial carbon bed adsorber, where
small amounts of aromatic organic compounds are removed. The vapor
leaving S-10 flows to C-11, a 3-stage compressor that increases the
process pressure to 300 PSIA. Heat exchanger module X-14 removes
the heat of compression cooling the vapor to 260.degree. C. In
practice, X-14 models the compressor first and second stage
intercoolers and the 3 stage after-cooler.
[0066] M-12 mixes the vapor from C-11 with superheated steam and
the combined flow enters the carbon monoxide shift converter, R-13.
The shift converter is modeled as an adiabatic reactor. This
reactor converts water and carbon monoxide to desired carbon
dioxide and hydrogen products. Energy is recovered in heat
exchanger, X-15. This energy is returned back to the process. The
water that condenses in X-15 is removed in vapor-liquid separator
F-16. The vapor from separator, F-16, flows to a pressure swing
adsorption unit where 80% of the hydrogen leaving F-16 is recovered
as product with 99.9% purity. The remaining vapor leaving the
pressure swing adsorption unit flows to the carbon dioxide recovery
system, module S-18. S-18 models the carbon dioxide recovery system
as a simple separation device. In practice this equipment could be
a membrane system or an amine system with a liquid carbonic and/or
dry ice production unit. The vapor leaving S-18 flows to heater,
H-20, preheating the vapor prior to feeding the rotary kiln.
[0067] A significant advantage of this process configuration with
the major recycle loop carrying the unconverted hydrogen and other
light gases from the PSA unit, is that these gases are further
converted in the steam/CO.sub.2 reforming units to make more
hydrogen product, as required in the mass balance dictating that
the hydrogen coming in with the feedstock must leave the process as
the hydrogen product. Additional or higher conversion stages in the
PSA unit are not needed when this recycle loop is used.
[0068] To validate the process simulation predictions, a biomass
sample of grape pomace, available in huge quantity from the wine
industry, was test-run in a pilot unit as illustrated in FIG. 2,
less the hydrogen purification and liquid carbonic steps, to
produce the syngas stream. This measured syngas stream was compared
with WinSim's Design-2 process simulation prediction below in Table
1.
Comparison of Pomace Produced Syn.sub.2 as with Simulation
Results
TABLE-US-00004 [0069] TABLE 1 Component Test Results Simulation
Prediction Hydrogen 59.4% 61.4% Oxygen + Argon* 0% Nitrogen* 0%
Carbon Monoxide 32.4% 31.3% Carbon Dioxide 2.96% 6.2% Methane 5.1%
Ethane, acetylene, ethylene 570 ppm <940 ppm Propane** 98 ppm
Butanes** 60 ppm Benzene** 198.4 ppm 1 ppb C7 and above** 380 ppm
Hydrogen Sulfide** 59.8 ppm Carbonyl Sulfide** 1.74 ppm Methyl
Mercaptan** 16.6 ppm Carbon Disulfide** 35.3 ppm *Air leakage
accounted for. **In practice, these components will be removed by a
zinc bed, carbon bed or are recycled to the kiln
[0070] The comparison of the test results and the simulation
prediction of syngas is excellent. The kiln and steam/CO.sub.2
reformer chemical reactors' process temperatures and steam content,
in the simulation, match those of the pilot demonstration.
[0071] The energy balance was completed in order to identify where
heat sources in the process can be used to provide the endothermic
heat needed for the steam reforming chemistry discussed above. In
the table below, it can be seen that the largest heat requirement
is for the steam/CO.sub.2 reforming kiln R-3 via heater H-2. The
second stage steam/CO.sub.2 reformer R-7 is supplied by induction
heaters or by DC electrical resistance heat estimated at about 600
kW. For a 20 dry ton/day feedstock plant, this heat requirement is
around 1200 kWt. This can be supplied by heat exchange-recovering
heat in X-8 from the very hot syngas leaving the second stage
steam/CO.sub.2 reformer R-7, which is about 1200 kW. There is also
heat available in X-15 from the exothermic CO shift unit that
further enhances the hydrogen production where this heat can be
used to drive a boiler to make the steam needed for the process. In
this way, only a small amount of grid electricity around 560-760 kW
is needed to drive the plant.
TABLE-US-00005 TABLE 5 Process Power Requirements Summary
Cellobiose Pomace Chemical Formula C12--H22--O11 C12--H16--O6 KW KW
Inputs Rotary Kiln 1189.41 1268.32 Steam Reformer 601.36 628.71
Compressors 207.12 276.21 Boiler 392.84 531.78 Product Purification
18.64 18.64 Outputs X-8 1292.01 1221.88 X-15 561.69 756.70 Total
Power Load 555.67 745.07 Hydrogen Production, Kg/Hr 93.86 131.42
Carbon Dioxide Production, Kg/Hr 1020.22 1319.61 Power Demand,
KW/Kg Hydrogen 5.92 5.67
The heat sources and heat demands are shown in Table 5 comparing
cellulose (cellubiose dimer) and grape pomace winery waste. And
they are very comparable.
* * * * *