U.S. patent application number 16/642560 was filed with the patent office on 2020-10-22 for systems and methods for refining coal into high value products.
This patent application is currently assigned to University of Wyoming. The applicant listed for this patent is John ACKERMAN, University of Wyoming. Invention is credited to John ACKERMAN, Carl BAUER, David BELL, Richard HORNER, John MYERS.
Application Number | 20200332197 16/642560 |
Document ID | / |
Family ID | 1000004972296 |
Filed Date | 2020-10-22 |
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United States Patent
Application |
20200332197 |
Kind Code |
A1 |
ACKERMAN; John ; et
al. |
October 22, 2020 |
SYSTEMS AND METHODS FOR REFINING COAL INTO HIGH VALUE PRODUCTS
Abstract
Described herein are integrated thermochemical processes for the
conversion of coal into high-value products using a combination of
pyrolysis and solvent extraction. The described systems and methods
are versatile and may be used to generate a variety of high value
products including chemicals (aromatics, asphaltenes, napthenes,
phenols, polyamides, polyurethanes, polyesters), polymer composite
products (resins, coatings), graphitic products, agricultural
materials, building materials, carbon fiber and other products that
are substantially more valuable that the energy generated via
combustion. Further, these systems and methods are specifically
designed to be highly branched and highly flexible, allowing for a
high selectivity and optimization for increasing the value of the
products relative to the feedstock.
Inventors: |
ACKERMAN; John; (Laramie,
WY) ; MYERS; John; (Laramie, WY) ; HORNER;
Richard; (Laramie, WY) ; BAUER; Carl; (South
Park, PA) ; BELL; David; (Laramie, WY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ACKERMAN; John
University of Wyoming |
Laramie
Laramie |
WY
WY |
US
US |
|
|
Assignee: |
University of Wyoming
Laramie
WY
|
Family ID: |
1000004972296 |
Appl. No.: |
16/642560 |
Filed: |
September 12, 2018 |
PCT Filed: |
September 12, 2018 |
PCT NO: |
PCT/US2018/050690 |
371 Date: |
February 27, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62557804 |
Sep 13, 2017 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 1/02 20130101; C10G
1/065 20130101; C10G 1/042 20130101; C10G 1/045 20130101; C10G
2300/4006 20130101; C10G 2300/4081 20130101; C10G 2300/4012
20130101 |
International
Class: |
C10G 1/04 20060101
C10G001/04; C10G 1/02 20060101 C10G001/02; C10G 1/06 20060101
C10G001/06 |
Claims
1. A method for converting coal into a plurality of high value coal
products and extracts comprising: providing a feedstock, wherein
said feedstock is at least partially derived from coal; processing
said feedstock, wherein said processing step includes a combination
of pyrolysis and solvent extraction, wherein said pyrolysis and
solvent extraction are integrated and carried out under conditions
for generating a plurality of high value coal products.
2. The method of claim 1, wherein greater than or equal to 50% by
mass dry basis of said high value coal products are liquid at
standard temperature and pressure.
3. The method of claim 1 or 2, wherein said step of processing said
step is highly branched and highly selective.
4. The method of any of claims 1-3, wherein said pyrolysis is
performed at a pressure selected from the range of 0.5 atm to 15
atm.
5. The method of any of claims 1-4, wherein said pyrolysis is
performed at a temperature selected from the range of 400.degree.
C. to 1200.degree. C.
6. The method of any of claims 1-5, wherein said pyrolysis is
performed in less than or equal to 5 seconds.
7. The method of any of claims 1-6, wherein said pyrolysis is
integrated with said solvent extraction.
8. The method of any of claims 1-7, wherein said pyrolysis
generates a mass percentage of gas of less than or equal to 25%,
excluding water vapor.
9. The method of any of claims 1-8, wherein said pyrolysis is
performed in the presence of hydrogen gas, methane, syngas or any
combination thereof.
10. The method of any of claims 1-9, wherein said pyrolysis is
flash pyrolysis.
11. The method of any of claims 1-10, wherein said solvent
extraction is performed with at least one liquid solvent.
12. The method of any of claims 1-11, wherein said at least one
solvent is selected from the group consisting of an aliphatic
solvent, an aromatic solvent, a polar solvent, a hydrogen donating
solvent, an ionic liquid solvent and any combination thereof.
13. The method of any of claims 1-12, wherein said solvent
extraction is performed with at least two liquid solvents.
14. The method of claim 13, wherein a first solvent is a polar
solvent and a second solvent is a hydrogen donating solvent or vice
versa.
15. The method of any of claims 1-14, wherein said solvent
extraction is a single stage solvent extraction, multiple single
stage solvent extractions, a single multistage solvent extraction,
multiple multistage solvent extractions or a combination of single
stage and multistage solvent extractions.
16. The method of any of claims 11-15, wherein said solvent
extraction is performed at a temperature less than the critical
temperature of said at least one solvent.
17. The method of any of claims 1-16, wherein said solvent
extraction is performed at less than or equal to 350.degree. C.
18. The method of any of claims 1-17, wherein said solvent
extraction generates a mass percentage of gas less than or equal to
5%, excluding water vapor.
19. The method of any of claims 11-18, wherein one of said at least
one solvents comprises tetralin (1,2,3,4-Tetrahydronaphthalene),
1-methyl-napthalene, toluene, dimethylformamide (DMF) or any
combination thereof.
20. The method of any of claims 1-19, wherein said solvent
extraction is performed upstream of said pyrolysis.
21. The method of any of claims 1-20, wherein said pyrolysis is
performed upstream of said solvent extraction.
22. The method of any of claims 1-21, wherein a portion of products
for said pyrolysis step are recycled to said solvent
extraction.
23. The method of claim 22, wherein said processing step comprises
multiple solvent extractions and products from a later solvent
extraction are recycled to an earlier solvent extraction or said
pyrolysis or used as an intermediate for upstream further
processing.
24. The method of any of claims 1-23, wherein said feedstock at
least partially derived from coal is greater than or equal to 90%
unrefined coal by weight.
25. The method of claim 24, wherein said unrefined coal is
physically, chemically or thermally preprocessed prior to said step
of processing.
26. The method of any of claims 1-25, wherein a portion of said
feedstock is one or more product streams from said pyrolysis, said
solvent extraction, recycle streams or a combination thereof.
27. The method of any of claims 1-26, wherein said feedstock at
least partially derived from coal comprises subbituminous coal.
28. The method of any of claims 1-27, wherein said feedstock is at
least partially derived from coal is derived from run of mine
coal.
29. The method of any of claims 1-28, wherein said high value coal
products comprise less than or equal to 10% fuel products.
30. The method of any of claims 1-29, wherein said high value coal
products comprise polymers or polymer precursors.
31. The method of any of claims 1-30, where said high value coal
products comprise polyurethane.
32. The method of any of claims 1-31, wherein said high value coal
products comprise composite polyurethane foam.
33. The method of any of claims 1-32, wherein said high value coal
products comprise polyamides.
34. The method of any of claims 1-33, wherein said high value coal
products comprise polyesters.
35. The method of any of claims 1-34, wherein said high value coal
products comprise adhesives.
36. The method of any of claims 1-35, wherein said high value coal
products comprise aromatics.
37. The method of claim 36, wherein said high value coal products
comprise benzene, toluene, xylene, phenols, cresols, xylenols,
naphthenols, C9 single aromatic rings, C10 single aromatic ring
isomers or any combination thereof.
38. The method of any of claims 1-37, wherein said high value coal
products comprise paraffins, olefins or a combination thereof.
39. The method of any of claims 1-38, wherein said high value coal
products comprise asphaltenes.
40. The method of any of claims 1-39, wherein said high value coal
products comprise coal tar, distillates, pitch, carbon fibers or
any combination thereof.
41. The method of any of claims 1-40, wherein said high value coal
products comprise soil amendments
42. The method of any of claims 1-41, wherein said high value coal
products comprise building materials.
43. The method of any of claims 1-42, wherein a significant portion
of said high value coal products are solids.
44. The method of claim 43, wherein said solids can be converted to
construction materials, composite materials, liquid additives or
any combination thereof when combined a resin, liquid or other
bi-product generated by the methods described in claims 1-43.
45. The method of claim 44, wherein said extracts can include
metals and rare earth elements.
46. A method for converting coal into a plurality of high value
coal products comprising: providing a primary feedstock at least
partially derived from coal; processing said primary feedstock,
wherein said processing sequence is: a pyrolysis step, wherein said
pyrolysis step is performed in less than or equal to 10 seconds
performed in a hydrogen rich atmosphere; and a solvent extraction
step, wherein said solvent extraction step is performed with at
least one liquid solvent, wherein said liquid solvent is selected
from the group consisting of: a polar solvent, a hydrogen donating
solvent and any combination thereof; wherein said pyrolysis step is
the first processes step performed on said primary feedstock and
said solvent extraction step is the second process step carried out
on a solid char produced from said pyrolysis step; and wherein said
pyrolysis step and said solvent extraction step are integrated and
carried out under conditions for generating a plurality of high
value coal products.
47. The method of claim 46, wherein said pyrolysis step is a flash
pyrolysis process.
48. The method of claim 46 or 47, wherein said solvent step process
is a single stage solvent extraction, multiple single stage solvent
extractions, a single multistage solvent extraction, multiple
multistage solvent extractions or a combination of single stage and
multistage solvent extractions.
49. The method of any of claims 46-48 wherein said solvent
extraction step uses two or more solvents.
50. The method of any of claims 46-49, wherein processing said
feedstock further comprises one or more separation steps occurring
after said pyrolysis step, after said solvent extraction step or in
between multiple solvent extractions.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application claims the benefit of and priority
to U.S. Provisional Patent Application No. 62/557,804 filed Sep.
13, 2017 which is hereby incorporated by reference to the extent
not inconsistent herewith.
BACKGROUND OF THE INVENTION
[0002] Coal mining and production represents a large, valuable
industry in both the United States and abroad. The vast majority of
this coal is combusted to generate energy. Currently, there is a
great deal of economic and political pressure on the building of
new coal-fired power plants. Accordingly, to further utilize coal
beyond combustion, it becomes increasingly attractive to
investigate use as a feedstock for other processes, including for
the production of chemicals, plastics, building materials and
products which may have significantly higher value than that of the
energy produced by power plants.
[0003] Research and development into coal as a feedstock for the
generation of chemicals and other materials has been around for
more than 50 years. Interest in this field has typically increased
during periods in which traditional petroleum feedstocks have
become expensive due to high oil prices, such as in the 1970's. For
example, U.S. Pat. No. 4,346,077 discusses pyrolysis of coal to
generate liquid hydrocarbons and vapors. U.S. Pat. No. 9,074,139
describes generation of aromatic compounds from coal utilizing
liquefaction and hydrocracking. Common amongst these references and
most coal conversion technology is that coal is being converted
into coal tars to mimic petroleum hydrocarbons in such a way that
it can then be processed through a petroleum refinery. Coal, which
generates a greater amount of solid products and typically contains
a high sulfur content and some metals, often makes a relatively
poor substitute for processes designed for oil-based
feedstocks.
[0004] It can be seen from the foregoing that there remains a need
in the art for systems and methods for the deliberate,
thermochemical conversion of coal into intermediate and finished
high-value products, thereby generating materials that are far more
valuable than the equivalent coal-based energy produced via
combustion. Further, separation and process systems and methods are
needed that are specifically tailored and/or customized to coal and
coal-based feedstocks to achieve effective transformation into
products, that consider yields, efficiency, conversion rates and
the manufacture of distinguished goods that can be sold.
BRIEF SUMMARY OF THE INVENTION
[0005] Described herein are integrated thermochemical processes for
the deliberate decomposition, extraction and conversion of coal
into high-value products and goods using a combination of pyrolysis
and solvent extraction. The described systems and methods are
versatile deliberate and may be used to generate a variety of
intermediate and finished high value products including chemicals
(aromatics, asphaltenes, napthalenes, phenols and precursors for
the production of polyamides, polyurethanes, polyesters, graphitic
materials), polymer composite products (resins, coatings,
adhesives), agricultural materials, building materials, carbon
fiber, graphene products and other materials that are substantially
more valuable that the energy generated via combustion. Further,
these systems and methods are specifically designed to be highly
branched (i.e. process steps that together are amenable to produce
wide ranging product types and specifications from the same
feedstock), as well as being synergistic (e.g. permitting combining
resin systems produced from coal with solid carbon material derived
from coal to make composite materials). Thus the systems and
methods are highly adaptive to markets and responsive to product
demand. Thus, allowing for a high selectivity and optimization for
increasing the value of the actual products relative to the
feedstock. Some of these products may be coal extracts such as
metals and rare earth elements.
[0006] The provided thermochemical processes convert a large
portion of the coal feedstock into and extracts from coal value
added products and may focus on converting a high percentage (e.g.
greater than 50% dry basis) of the solid material into fluids.
These systems and methods may avoid expensive, energy intensive
hydrocracking and hydrotreating processes. The thermochemical
processes described herein use an integrated combination of thermal
and chemical processes to provide controlled and deliberate
conversion of coal and extraction from coal into a selective and
switchable mix of high-value products that may be optimized to
achieve profitable manufacturing motivated by the total value of
goods generated.
[0007] In an aspect, provided is a method for converting coal into
a plurality of high value coal products comprising: i) providing a
feedstock, wherein the feedstock is at least partially derived from
coal; ii) processing the feedstock, wherein the processing step
includes a combination of pyrolysis and solvent extraction, wherein
the pyrolysis and solvent extraction are integrated and carried out
under conditions for generating a plurality of high value coal
products. The percentage of high value coal products that are
liquid at standard temperature and pressure may be greater than or
equal to 50% dry basis, greater than or equal to 60%, or
optionally, greater than or equal to 70%. The step of processing
may be highly branched, discriminating and wide ranging, yet highly
selective.
[0008] Pyrolysis is generally used in the described systems to
reduce the size or length of the complex molecules commonly found
in coal and to concentrate extracts. Pyrolysis as described herein
may refer to flash pyrolysis, for example, having small residence
times (on the order of seconds) at high temperatures. The pyrolysis
processes described herein may, in some embodiments, specifically
exclude the use of a catalyst and, in some embodiments,
specifically include the use of a catalyst. The pyrolysis processes
described herein may, in some embodiments be highly selective.
[0009] Pyrolysis may be a single stage pyrolysis, multiple single
stage pyrolysis, a single multistage pyrolysis, multiple multistage
pyrolysis or a combination of single stage and multistage pyrolysis
steps. Each pyrolysis or pyrolysis step may independently be
performed at a pressure selected from the range of 0.5 atm to 15
atm, 0.9 atm to 15 atm, or 0.9 atm to 10 atm. Each pyrolysis or
pyrolysis step may be performed at a temperature selected from the
range of 400.degree. C. to 1200.degree. C., 750.degree. C. to
1200.degree. C., or optionally, 900.degree. C. to 1100.degree. C.
In an embodiment, the residence time for pyrolysis is selected over
the range of 30 minutes to 0.1 seconds and optionally less than or
equal to 10 seconds, 5 seconds, 2 seconds, or 1 second. Pyrolysis
may be integrated with solvent extraction, as a pretreatment or
post treatment. In each pyrolysis or pyrolysis step may
independently be performed at a pressure selected from the range of
0.5 atm to 15 atm, 0.9 atm to 15 atm, or 0.9 atm to 10 atm.
[0010] Solvent extraction may generate a mass percentage of gas,
excluding water vapor, less than or equal to 25%, less than or
equal to 15%, less than or equal to 10%, less than or equal to 5%,
or optionally, less than or equal to 3%. Solvent extraction may
generate a mass percentage of liquid, which may include or exclude
the solvent itself up to 100%, which itself becomes a precursor or
intermediate for further processing into goods and products.
Pyrolysis may be performed in nitrogen, air or hydrogen-donating
environment such as in the presence of hydrogen gas, methane,
syngas or any combination thereof. Pyrolysis may be flash
pyrolysis.
[0011] Solvent extraction is generally used to remove and/or
separate various components of the solid feedstock including the
intermediates and end products. It should be noted, that in some
instances solvent extraction does facilitate chemical reactions
including conversion of solid material into liquids and may
chemically alter the various components being processed. Various
solvents known in the art may be used, including aliphatic,
aromatic, hydrogen donating, non-polar solvents, polar solvents and
ionic liquid solvents. Solvent extraction may include multistage
extraction and multiple solvent extraction steps ahead or following
pyrolysis. Solvent extraction may include super critical fluid
steps. Solvent extraction may also utilize fractionation, or the
use of multiple solvent extraction steps at different temperatures
and pressures. Various uses of solvent recovery, including solvent
recycling may provide additional efficiency and cost savings in
addition to the solvent being a precursor or intermediate product
for further processing in itself.
[0012] Solvent extraction, as described herein, may be performed
with at least one liquid solvent. The at least one solvent may be
selected from the group consisting of an aliphatic solvent, an
aromatic solvent, a polar solvent, a hydrogen donating solvent, an
ionic liquid solvent and any combination thereof. Solvent
extraction may use at least two liquid solvents. The first solvent
may be a polar solvent, a combination of solvents which may include
polar and aromatic solvents applied separately. The second solvent
may be a hydrogen donating solvent or vice versa. The solvent
extract itself may be an intermediate that is further processed
into a finished product.
[0013] Solvent extraction may be a single stage solvent extraction,
multiple single stage solvent extractions, a single multistage
solvent extraction, multiple multistage solvent extractions or a
combination of single stage and multistage solvent extractions.
Solvent extraction may be performed at a temperature less than the
critical temperature of the solvent. Each Solvent extraction or
step may independently be performed at less than or equal to
400.degree. C., less than or equal to 350.degree. C., or
optionally, less than or equal to 300.degree. C. Solvent extraction
may generate a mass percentage of gas, excluding water vapor, less
than or equal to 10%, less than or equal to 5%, or optionally, less
than or equal to 1%.
[0014] Solvents as described herein may comprise tetralin
(1,2,3,4-Tetrahydronaphthalene), 1-methyl-napthalene, toluene,
dimethylformamide (DMF) or any combination thereof. A solvent may
be impure, for example, due to recycle or separation
inefficiencies.
[0015] The described systems and method are flexible and the
solvent extraction step may be performed prior to the pyrolysis
step and vice versa. Further, systems that are more complex may
utilize multiple pyrolysis steps and/or multiple solvent extraction
steps in any combination, for example, a first pyrolysis step
followed by a first solvent extraction and then a second pyrolysis
step. Additionally, recycle streams may be utilized such that a
portion the output from one step (either pyrolysis or solvent
extract) may be recycled and used as in input or as a portion of an
input for a previous step, subsequent step or current step. The
solvent extraction and pyrolysis steps may be considered as
integrated achieving results that pyrolysis and/or solvent
extraction cannot achieve alone.
[0016] The solvent extraction may be performed upstream of the
pyrolysis. The pyrolysis may be performed upstream of the solvent
extraction. A portion of products from the pyrolysis step may be
recycled to the solvent extraction. A portion of products from the
solvent extraction may be recycled to the pyrolysis or sent for
further downstream processing. The processing step may comprise
multiple solvent extractions and solvents from a later solvent
extraction may be recycled to an earlier solvent extraction or the
pyrolysis step.
[0017] The primary feedstocks described herein are generally coal
or coal-based, including run of mine coal and/or coal, which may be
physically, chemically and/or thermally pre-processed which may
include drying and vapors recovery. Pre-processing may include
pulverizing, de-ashing and/or drying. The described systems and
methods are flexible and may be used with any primary feedstock
including lignite, subbituminous and bituminous coal. Secondary
feedstocks inclusions may include other hydrocarbon sources such as
biomass and oil shale and/or inclusion of secondary recycle streams
from downstream processes e.g. syngas and other reactive mineral
resources such as trona.
[0018] High value coal products described herein have a monetary or
economic value significantly higher than the value of the energy
produced by burning or combusting the primary feedstock. High value
coal products may comprise a minority manufacture of fuels products
and/or blending components, such as less than or equal to 10% fuel
products and/or blending products, less than or equal to 5% fuel
products and/or blending products, or optionally, less than or
equal to 3% fuel products and/or blending products. High value coal
products may comprise polymers or polymer precursors. High value
coal products may comprise polyurethane. High value coal products
may comprise composite polyurethane foam. High value coal products
may comprise polyamides. High value coal products may comprise
polyesters. High value coal products may comprise aromatics. High
value coal products comprise benzene, toluene, xylenes (including
isomers), phenols, cresols, xylenols (including isomers),
naphthenols, C9 single ring aromatics (including isomers), C10
single ring aromatics (including isomers) or any combination
thereof. High value coal products may comprise paraffins, olefins,
asphaltenes, napthenes or a combination thereof. High value coal
extractive products may include metals and rare earth elements.
[0019] High value coal products may comprise asphaltenic
intermediates and/or finished products. High value coal products
may comprise road paving and roofing intermediates, additives or
finished products. High value coal products may comprise coal tar,
distillates, pitch, asphalt, graphitic materials, carbon fibers or
any combination thereof. High value coal products may comprise soil
amendments and fertility products. High value coal products may
comprise building materials. A significant portion of the high
value coal products may be solids, for example, greater than or
equal to 10% solids, greater than or equal to 20% solids, or
optionally, greater than or equal to 30% solids. The solids may be
converted to graphitic materials, construction materials, composite
materials, liquid additives or any combination thereof when
combined a resin, liquid or other bi-product generated by the
methods described herein. High value products may include syngas,
urea, CO.sub.2 and/or acetylene.
[0020] In an aspect, provided is a method for converting coal into
a plurality of high value coal products comprising: i) providing a
primary feedstock at least partially derived from coal; ii)
processing the primary feedstock, wherein the processing sequence
is a) a pyrolysis step, wherein the pyrolysis step is performed in
less than or equal to 10 seconds performed in a hydrogen rich
atmosphere; and b) a solvent extraction step, wherein the solvent
extraction step is performed with at least one liquid solvent,
wherein the liquid solvent is selected from the group consisting
of: a polar solvent, and/or a hydrogen donating solvent and/or any
combination thereof; c) wherein the pyrolysis step is the first
process step carried out on the primary feedstock and wherein the
solvent extraction process is the second process step carried out
on the solid char produced from the pyrolysis; d) wherein the
pyrolysis and solvent extraction process are integrated and carried
out under conditions for generating a plurality of high value coal
products.
[0021] The pyrolysis step may be a flash pyrolysis process. The
solvent extraction step may be a single stage solvent extraction,
multiple single stage solvent extractions, a single multistage
solvent extraction, multiple multistage solvent extractions or a
combination of single stage and multistage solvent extractions. The
solvent extraction step may use two or more solvents. Processing
the feedstock may further comprise one or more separation steps
occurring after the pyrolysis, after the solvent extraction process
or in between multiple solvent extractions.
[0022] Without wishing to be bound by any particular theory, there
may be discussion herein of beliefs or understandings of underlying
principles relating to the devices and methods disclosed herein. It
is recognized that regardless of the ultimate correctness of any
mechanistic explanation or hypothesis, an embodiment of the
invention can nonetheless be operative and useful.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
[0023] FIG. 1 provides an overview of the described process
including additional post-processing to generate liquid and solid
products.
[0024] FIG. 2 provides an example processing step where pyrolysis
is followed by solvent extraction.
[0025] FIG. 3 provides an example of a multistage solvent
extraction step where two different solvents are used to increase
extraction effectiveness.
[0026] FIG. 4 provides an overview including inputs and
outputs.
[0027] FIG. 5 is an example of a highly branched, highly selective
process utilizing solvent extraction and pyrolysis.
[0028] FIG. 6 is an example of a highly branched, highly selective
process utilizing solvent extraction and pyrolysis.
[0029] FIG. 7 provides an example overview with high detail
regarding products and additional processes.
[0030] FIG. 8 provides additional examples of integrated,
multistage processing steps.
[0031] FIG. 9 provides example thermochemical processing steps.
DETAILED DESCRIPTION OF THE INVENTION
[0032] In general, the terms and phrases used herein have their
art-recognized meaning, which can be found by reference to standard
texts, journal references and contexts known to those skilled in
the art. The following definitions are provided to clarify their
specific use in the context of the invention.
[0033] As used herein, "feedstock at least partially derived from
coal" refers to a solid, powder, slurry, liquid, fluid or other
material that has been generated from a raw coal source. For
example, raw coal may be crushed into a powder prior to processing.
The feedstock may have various physical, thermal and chemical
pretreatments known in the art to further facilitate processing of
the feedstock, for example, by flash pyrolysis and solvent
extraction. The feedstock may also act as a recycled stream from
one or more of the downstream processes or intermediates (e.g.
solid material remaining after solvent extraction) so that
additional products, such as liquid products, may be promoted by
reprocessing less valuable or unwanted intermediate products.
[0034] "Coal" refers to predominately solid hydrocarbons that may
contain some amount of fluid material. Coal is generally composed
of hydrogen, carbon, sulfur, oxygen and nitrogen. Coal, as
described herein, may refer to bituminous coal, subbituminous coal
and lignite. Coal may also refer to ash or peat.
[0035] "Flash Pyrolysis" as described herein, refers to a thermal
process in which a feedstock or intermediate product is exposed to
sufficient energy to rapidly heat the feedstock or intermediate.
Flash pyrolysis may, for example, provide heat or heat the material
being processed to temperatures of greater than 750.degree. C.,
greater than 900.degree. C., greater than 1050.degree. C., or
optionally, greater than 1200.degree. C. Flash pyrolysis may refer
to a heating or resonance time of less than 60 seconds, less than
10 seconds, less than 5 seconds, less than 1 second, or optionally,
less than 0.5 seconds. Flash pyrolysis may be performed in a
vacuum, in the presence of air, or optionally, in the presence of a
purified gas such as hydrogen or methane or syngas. It may also be
performed in an inert atmosphere notably at very high temperatures
greater than 1200.degree. C.
[0036] "Solvent extraction" refers to the process of flowing a
liquid solvent through or across a feedstock or intermediate
product to facilitate the extraction components of the material via
chemical reaction and/or mass transfer via solubility in the
solvent. As described herein, solvent extraction may utilize one or
more solids in one or more solvent extraction steps, including in
multistage solvent extractions in which the same or similar
solvents are repeatedly used on a materials. Solvents, as described
herein, may be mixtures including mixtures of liquid hydrocarbons
generated by the processes described herein. Solvents, as described
herein, may be mixtures of a number of solvents. Solvents may be
recycled and reused as is known in the art. Solvent extraction may
be at subcritical temperatures. Solvent extraction may be performed
at reduced pressures, atmospherics pressures or increased
pressures.
[0037] "Solvent" as described herein refers to a liquid or a
mixture of liquids or cocktails having solubility with regard to
hydrocarbons or other species and molecules present in coal.
Solvent may refer to a complex mixture of liquids, including
hydrocarbon mixtures generally defined by boiling point ranges.
Solvents may be polar, paraffinic, aromatic, alcohol, ionic, and/or
hydrogen-donating in nature. In embodiments utilizing two or more
solvents, solvents may be distinguished by composition, additives,
molecular design, boiling point ranges or a combinations
thereof.
[0038] "High Value Coal Products" describe chemicals and materials
(both solid and liquid) generated by the processes described herein
that are more valuable than the coal or feedstock at least
partially derived from coal. High value coal products may refer to
liquid products generated from predominately solid coal. The high
value coal products described herein may have a 1.5.times.,
2.times., 3.times., 5.times., 10.times., or optionally, at least
50.times. monetary value in comparison with the coal or raw coal
material provided in the feedstock. High value coal products may
refer coal products that are 1.5.times., 2.times., 3.times.,
5.times., 10.times., or optionally, at least 50.times. more
valuable than the energy that would be produced via burning of the
coal. High value coal products may refer to products that are not
fuel (e.g. created for the purpose of burning to generate energy).
Examples of high value coal products include polymers (e.g.,
polyurethane, polyesters, polyamides), high value chemicals (BTX,
paraffins, olefins, asphaltenes), composite materials, carbon
fiber, graphene, building materials, road, paving and roofing
materials and soil amendments. High value coal products may
represent a fraction of the total material converted from the
feedstock, for example, 50% of the total products on a dry basis,
70% of the total products on a dry basis, 80% of the total products
on a dry basis, or optionally, 90% of the total products on a dry
basis.
[0039] "Hydrogen rich environment" refers to an atmosphere
comprising a large composition of hydrogen gas. Hydrogen rich
environment may refer to an atmosphere comprising greater than or
equal to 50 mole percent hydrogen, or in some embodiments, greater
than or equal to 70 mole percent hydrogen. Hydrogen rich
environment may refer to the atmosphere or conditions of a chamber
or vessel in which pyrolysis is performed.
[0040] "Inert atmosphere" refers to an environment in which the gas
phase is chemically inactive with the feedstock(s) present.
[0041] Pressure values described herein are provided as absolute
pressure values, unless otherwise indicated.
[0042] The following examples further illustrate the invention but,
of course, should not be construed as in any way limiting its
scope.
Example 1--Coal Refining Process Overview
[0043] This example demonstrates a high-level overview of methods
for the thermochemical decomposition of coal or a coal-based
feedstock into deliberately selected high value products. FIG. 1
provides an overview schematic. In FIG. 1, a feedstock at least
partially derived from coal is feed into a processing step 100 that
comprises pyrolysis and solvent extraction. Generally, the steps of
pyrolysis and solvent extraction may occur in any order and may
include multistage processes, additional steps of pyrolysis and/or
solvent extraction, recycle streams and separations. From a process
and method perspective, the solvent extraction and pyrolysis steps
are integrated. The primary processing step 100 generates at least
one solid output and liquid output, but may generate multiple solid
and liquid output streams based on the configuration of the primary
processing step 100. In some cases, liquids will undergo additional
liquid processing 102, with the option of liquid recycle streams
106 returning specific liquid fractions to the primary processing
100. In some cases, liquid recycle streams 106 including solvent
recycle streams may be useful as intermediates to downstream
processes or as products and may be separately sold or processed.
Similarly, solids may under additional solid processing 104, with
optional recycle streams 104. The end result is at least one high
value liquid product and at least one high value solid product,
although typically the described processes will generate a variety
of high value products as well as lower value products (relative to
feedstock cost) which may or may not be re-processed or sold.
[0044] An example of the processing step 100 is provided in FIG. 2.
First, the coal-based feedstock is treated via pyrolysis 200 reduce
carbon chain length and liquefy or vaporize a portion of the
feedstock. In this example, pyrolysis is performed at
400-1200.degree. C. and at atmospheric pressure. Flash pyrolysis
(e.g. resonance time of less than 1 minute) or pyrolysis with low
resonance times (e.g. less than 15 minutes) may be used to increase
efficiency, change product make and yields and/or decrease
processing time while reducing energy requirements and, therefore,
costs. The fluids from the pyrolysis process 200 may be either
further processed (e.g. separated, polymerized, etc.) in downstream
operations. The solids from the pyrolysis process 200 are sent to a
solvent extraction unit 210. Solvent extraction 210 further removes
fluid components from the solid materials and may provide some
chemical reaction such as reducing carbon chain length, increasing
the ratio of hydrogen/carbon or interacting with sulfur and oxygen
bonds and recovery of metals and rare earth elements. Remaining
solids from the solvent extraction step 210 may be further treated
as described herein, recycled through the process for additional
conversion into lighter compounds or converted into other high
value products. The fluid stream from the solvent extractor 210 may
be separated, for example, in a distillation column 220. The fluid
stream may be split into one or more product streams based on
volatility and solvent may be recovered and returned to the solvent
extractor 210. FIG. 8 provides additional examples of integrated,
multistage processing steps and further illustrates the versatility
in ordering of the various process steps.
Example 2--Pyrolysis
[0045] Pyrolysis used in the described systems and methods provides
for the thermal decomposition of complex hydrocarbons found in coal
and helps convert a portion of the solid coal materials into
liquids and vapors. Pyrolysis as described herein is generally
performed at a high temperature while being low enough to avoid
combustion, for example, greater than 400.degree. C., greater than
800.degree. C., or optionally, greater than 1000.degree. C.
Further, to increase efficiency and reduce energy costs, pyrolysis
of the described methods has generally low residence times, for
example, less than 1 hour or in some cases less than 15 minutes.
Some embodiments of the present invention utilize flash pyrolysis
which may have a residence time less than 1 minute, or preferably
less than 15 seconds. The described pyrolysis steps may be
performed at or near atmospheric pressure or in a pressurized
environment, including in some embodiments, in the presence of a
hydrogen-rich gas including hydrogen gas, methane, natural gas or
syngas.
[0046] Specific pyrolysis parameters are dependent on the input or
feed stream. For example, in embodiments where pyrolysis is the
first step in the described methods, the feed will be primarily
coal or coal-derived material. However, in cases in which one or
more solvent extractions are performed, the remaining solid
material may have significantly different compositions and process
parameters will need to be altered accordingly.
[0047] Coal pyrolysis experiments were performed on Cordero Rojo
sub-bituminous coal. 25 g of coal was dried overnight at
100.degree. C. under argon. The dry coal weight was determined and
this becomes the basis for the yield calculations below. Then the
contents were heated to 500.degree. C. in a vertical tube furnace
for 40 minutes. The generated pyrolysis vapors were sent to a cold
trap at 0.degree. C. to condense the tars and vent the remaining
gas.
[0048] Below are weight-based yield results for dry coal based on
the experimental procedure above:
TABLE-US-00001 TABLE 1 Weight-based yield results for pyrolysis
Yield % Notes Solid Char 79.1 Char Weight * 100 Yield % Dry Coal
Weight Tar (liquid) 10.5 Cold Trap Liquid Tar Weight * 100 Yield %
Dry Coal Weight Gas Yield % 10.4 By difference
Example 3--Solvent Extraction
[0049] Solvent extraction provides an effective, cost efficient way
to recover desirable and valuable fluid components from a
predominately solid feedstock or intermediate. Additionally,
selection and design of solvents may provide some chemical
reactivity and may reduce the size or length of the complex
hydrocarbon molecules often found in coal and or permit the
economic recovery of metals and rare earth elements.
[0050] A variety of solvents are useful for the treatment of
coal-based feedstocks or intermediate coal products (e.g.
post-pyrolysis). Polar solvents, hydrogen donating solvents,
aliphatic solvents, aromatic solvents, ionic liquid solvents and
supercritical fluid extraction (including other solvents) all allow
for high flexibility in promoting the production of certain
products or product types and changes in solvent systems or
processes parameters can account for differences between various
coal feedstocks and types. The temperature and pressure of solvent
extraction is often tied to the solvent being used, but both
subcritical and supercritical solvent extraction may be
implemented.
[0051] Multiple solvent extractions with different solvent systems
and/or process parameters allows for higher efficiency in
converting solid material into more easily processed and
potentially more valuable fluid outputs. An example of multiple
single stage solvent extractions is provided in FIG. 3. A feed 201
(which may be a coal-based feedstock, a pyrolysis product or an
intermediate that has undergone multiple process steps, including
both pyrolysis and solvent extraction) is provided into a first
solvent extractor 210. The solvent extractor 210 uses a specific
solvent type, for example, a polar solvent to target certain coal
components such as aromatics. The first extract is then split in
one or more separation steps 220, such as a distillation column,
resulting in both a light fluid output and a heavy fluid output.
Solvent may be recycled back into the solvent extractor 210. The
solids remaining after the solvent extraction 210 are then
processed in a second solvent extraction process 211 that uses a
different solvent type, for example a hydrogen donating solvent, to
extract additional fluids remaining in the solids. Importantly, the
order of solvent extraction processes may be reversed or altered to
increase the quantity of certain hydrocarbons allowing for diverse
product selection. The extract from the second solvent extraction
211 is also fed to a separation step or steps 221, providing both a
light and heavy fluid output and the ability to recycle solvent.
Solids remaining after the multistage solvent extraction may be
further processed (e.g. pyrolysis or additional solvent extraction)
or may be processed as solid products as described herein.
[0052] Multistep solvent extractions, wherein a single solvent is
applied multiple times to increase total extraction, and
fractionation, wherein a single solvent is applied at different
temperatures may also be utilized in some embodiments.
[0053] Solvent extraction experiments were performed to examine the
extraction efficiency of tetralin and 1-methyl-naphthalene with
Cordero Rojo sub-bituminous coal (the same coal as described in
Example 2 and Table 1). The experimental procedure was to dry coal
for 36 hours at 90.degree. C. under a flowing argon stream; this
resulted in coal having <1% (wt) moisture. After drying, the dry
coal is weighed and this becomes the basis for the yield
calculations below, assuming 0% moisture. Approximately 100 g of
coal was placed in a pressure vessel which was then placed in an
oven. The desired solvent is pumped at a rate of 0.1 ml/g dry coal
per minute and to a pressure above the boiling point at the desired
temperature. The oven is turned on and the vessel is heated to a
controlled 360.degree. C. The solvent flow continues for 2 hrs
after this temperature is reached. Insignificant (assumed zero) gas
flows were noted. After 2 hrs, the solvent flow is stopped and the
oven turned off, thus allowing the vessel to cool. The pressure
drops to atmospheric. After cooling to below the boiling point of
the solvent, argon is flowed through the vessel for 36 hrs to
remove remaining solvent from the solid residue. The resulting
residue is weighed to determine the yield.
[0054] Below are weight-based yield results for dry coal based on
the experimental procedure above:
TABLE-US-00002 TABLE 2 Weight-based yield results for solvent
extraction 1-Methyl- Solvent Tetralin Naphthalene Notes Solid
Residue 53.3% 71.2% Residue Weight * 100 Yield % Dry Coal Weight
Extract Yield % 46.7% 28.8% By difference; solvent free basis
Example 4--Integrated Thermochemical Processing
[0055] The solids collected from the pyrolysis (Example 2) and the
solvent extraction (Example 3) experiments were then subjected to
the second processing option. In other words, solvent extraction
solid residue was pyrolyzed and pyrolysis char was solvent
extracted. Refer to FIGS. 1, 2 and 8.
[0056] The solvent extraction experimental procedure and conditions
were the same as described in the Solvent Extraction (Example)
except that no drying was required.
[0057] The pyrolysis experimental procedure and conditions were the
same as described in the Pyrolysis Example except that no drying
was required.
[0058] Below are weight-based tetralin solvent extraction yield
results for dry pyrolysis char based on the experimental procedure
above:
TABLE-US-00003 TABLE 3 Weight-based yield results for pyrolysis
followed by solvent extraction Solvent Tetralin Notes Solid Residue
97% Residue Weight * 100 Yield % Dry Char Weight Extract Yield % 3%
By difference; solvent free basis
[0059] Below are weight-based pyrolysis yield results for dry
tetralin-based solvent extraction residue based on the experimental
procedure above:
TABLE-US-00004 TABLE 4 Weight-based yield results for solvent
extraction followed by pyrolysis Yield % Notes Solid Char 86.1%
Char Weight * 100 Yield % Dry Solvent Residue Weight Tar (liquid)
5.5% Cold Trap Liquid Tar Weight * 100 Yield % Dry Solvent Residue
Weight Gas Yield % 8.4% By difference
[0060] Below are the combined 2-step process overall weight-based
yield results based on the results above plus results from coal
pyrolysis and coal solvent extraction examples. The solvent used
was tetralin.
TABLE-US-00005 TABLE 5 Weight-based yield results comparison
Solvent Extraction then Pyrolysis then Solvent Pyrolysis Yield %
Extraction Yield % Solid Char 46 77 Yield % Tar + Extract 50 13
(liquid) Yield % Gas Yield % 4 10
[0061] It should be noted that in both cases the tar yields from a
two-step process is greater than from pyrolysis-only or solvent
extraction-only processes.
Example 5--Branching Processes
[0062] By including additional processing steps, including steps
after the combination of pyrolysis and solvent extraction produces
a highly branched process which can result in a range of products
yielded or different specifications and functionality for the same
family of product types made. These additional processes convert
intermediate products resulting from thermochemical treatment
(noted in FIG. 2). The final product manufacturing processes
(formulations) which are fed by intermediates provide
high-selectivity an ability to make amounts of product that exhibit
performance that ensure economic stability with adjustments to
product flows and conditions that permit meeting product-based
market demand.
[0063] FIG. 9 provides an example of a highly branched, highly
selective process with additional post processing to generate
various high-value and useful products. The described process
consists of 3 stages which are integrated: thermal and chemical
decomposition, vapor-liquid separations, and product
manufacture/formulation which can be a single direct process or the
production of an intermediate product before further processing to
make the high value derivative or end product.
[0064] The thermal and chemical decomposition section consists of a
minimum of 2 processing steps, pyrolysis and solvent extraction,
with the possible addition of further post treatment steps, which
are performed in series. This process provide the maximum liquid
intermediate yields (from the separations section) which are the
primary feeds to vapor-liquid product manufacturing or
formulations. The thermal and chemical decomposition step consists
of pyrolysis followed by solvent extraction of the pyrolysis char
or of solvent extraction of the primary feedstock followed by
pyrolysis of the solvent extraction solid residue. Pyrolysis is the
direct or indirect heating of primary feedstock or solvent
extraction residue, in a neutral or hydrogen-donor atmosphere (such
as hydrogen-rich gas, syngas, or methane). Gas and solid products
result from pyrolysis. Solvent extraction consists of contacting
the primary feedstock or coal-pyrolysis char which can be multiple
steps and with different solvents. Solvents are recovered in the
separations section and a solvent-rich stream recycled to solvent
extraction. Solvent carried over into the next processing step is
minimized. Solvent extraction produces little gas, operates at
temperatures below pyrolysis temperatures, and produces a solvent
containing extract liquid stream and a solid residue stream. FIG. 8
illustrates the integrated thermal and chemical decomposition
step.
[0065] The separations section processes the vapor and liquid
intermediates from the thermal and chemical decomposition section
to make intermediates which feed for the product formulations
section. Depending upon the type of atmosphere in the pyrolysis
reactor, gases from the separations section may be processed and
recycled to the pyrolysis reactor. A solvent-rich stream will be
recovered in the separations section and recycled to the solvent
extraction section or used as an intermediate product for further
processing into a finished product. The separations section will
depend upon both the conversion section (temperature, pressure,
processing order, pyrolysis atmosphere, and solvent scheme) and the
product formulation sections. Pyrolysis vapors and solvent
extraction extract may be combined to feed a single separations
section or they may feed separate, parallel separation sections,
depending upon which high-value products are deliberately selected
and which will be byproducts or co-products. A distillation tower
may be the first unit operation in the separations section to
remove gaseous products from the thermal and chemical decomposition
section and produce various liquid intermediate. Side strippers and
side absorbers may be present. The bottoms (residue products) from
this first tower will be capable of being sent to a high-vacuum
distillation tower to further refine the heaviest material.
Depending upon product formulations specifics, the liquid
intermediates may be further separated or processed to produce a
desired intermediate feed for a specific product formulation. These
downstream separations could consist of adsorption, fractionation,
crystallization, azeotropic fractionation, extractive distillation,
liquid-liquid decanting and extraction, including combinations of
these. Unused (for product formulations) intermediates (for
example, intermediates with a higher boiling point range) may be
recycled to the thermal and chemical decomposition section to
further process this material into a more usable intermediates.
[0066] Product formulations consists of two main sub-sections:
intermediate (liquid) and gas product formulations and solids,
which are processed in post treatment formulations to make final
products. The final formulations will process the intermediates
from the separations section to produce 2-10 high-value products
and possibly additional lower-value products. Examples of these
high-value products can be petrochemicals, carbon fibers, polymers,
composites, asphaltenes, binders, coke, and others. Each of these
high-value products will be produced in a separate processing unit
using a customized feed from the separations section. The solids
from the thermal and chemical decomposition section will be sent to
solids formulations. Again, several products will be made in
separate processing units. Examples of lower value products include
water, minerals and clays together with flue gas. Examples of high
value product extracts include metals and rare earth elements.
[0067] The processes described herein are somewhat analogous to a
crude oil refinery, which is fed crude oil and where there are
multiple conversion steps, many separations (especially
fractionation) steps, many intermediates produced, and a multitude
of derivative products, generally made using distillation as a
primary process step to make intermediates followed by discrete
hydrocracking, hydrotreating and hydroprocessing to make finished
products. However, the described processes herein are specifically
tailored for a solid, high carbon content feedstock requiring a
distinct and unique integration of thermochemical processes, and
which generate a significant volume of solid high value products,
liquid products which either technically or economically or both
cannot be derived in a petroleum refinery and conversely generates
a small volume of fuel products and/or fuel blending
components.
[0068] FIGS. 5-7 provide more detailed examples of potential
process integrations to provide specific examples of high value
products. In FIG. 7, a coal based feed stock in placed into a dryer
to remove about 90% of water content. Next, the dried coal is
converted in the thermochemical processing step, in this example
consisting of two solvent extraction steps and a single pyrolysis
step which are fully integrated. The first solvent extraction
utilizes a polar solvent (e.g. DMF, ethanol, water) to recover
oxygen containing molecules. The second solvent extraction uses a
non-polar solvent (e.g. mixed hydrogenated oils, tetralin,
supercritical fuels, 1-methyl-naphthalene). Pyrolysis of the
solvent extraction residue is performed at 400-1200.degree. F. to
produce soil amendment products and building materials together
with valuable hydrocarbon containing vapors as intermediates for
further processing.
[0069] After thermochemical processing, the various streams are
separated by known techniques including, for example, distillation,
vacuum distillation, solvent extraction, crystallization, wipe-film
evaporation, liquid-liquid extraction and decanting. In some
embodiments, products which are separated may be recycled to the
thermochemical processing step until a desired composition,
conversion or boiling point range has been achieved. In some cases,
separations may be performed between thermochemical processing
steps (i.e. solvent extraction 1-separations-pyrolysis-solvent
extraction 2). For tar streams, vacuum distillation may be used to
generate various products based on the boiling point of the stream.
Fuel gasses coming off the separations step(s) may be processed in
a gas clean up step, such as amine treatments, scrubbing or
membrane filtering to remove undesirable gases (e.g. carbon dioxide
and SOx and NOx pollutants). After cleaning, fuel gases may also be
further converted using dry methane reforming (DMR) or steam
methane reforming (SMR) and deployed in the processing steps or
sold.
[0070] Solid products from the thermochemical processing steps may
be formulated into finished products or used as intermediates from
which finished products can be manufactured or sold. Examples
products include carbon filler byproduct for building materials,
further processing to produce activated-carbon products for
environmental management or used to make soil amendments or further
calcined to produce coke.
Example 6--Branching from Thermochemical Coal Processing
[0071] With reference to FIGS. 5 and 6 and this Example
demonstrates how thermochemical processing of coal can be adapted
and is flexible to produce a multitude of distinctive product
manufacturing outcomes based upon the unique integrated and
synergistic operation of the thermochemical process defined herein.
The examples describe laboratory scale experiments that demonstrate
proof of concept and viability of additional conversion of coal
based materials into high demand and high value products.
Coal Exfoliates
[0072] Described are coal solids from which polar and non-polar
molecules have been extracted with highly exfoliated properties and
high surface area form, which may be used as soil remediation
additives, gas/fluid absorbents, graphene oxide spray slurries, and
chars for gasification and hydrogenation.
[0073] Experimentally, a two-step experimental process including:
1) Removal of polar molecules via a continuous extraction using DMF
at 140.degree. C. @1 atm and 2) Removal of non-polar molecules via
supercritical CO.sub.2 extraction at 40.degree. C. @ 75 atm. The
two steps can be applied in any order.
Room Temperature Urethane Foam Composite Synthesis
[0074] Described are organic composite materials consisting of an
organic matrix filled with reinforcing particles with sufficient
structural strength to act as fillers in skin/matrix structural
composites or as freestanding foams for acoustic modulation,
thermal insulation, ballistic impact mitigation or buoyancy. These
coal based functionalized carbon particles together with a coal
derived urethane matrix may produce a low cost polymeric matrix
composite (PMC) with highly desirable properties.
[0075] Described herein is a process that produces urethane
composites from organic coal extracts without intermediate
separation of the extract into its individual chemical or boiling
point range constituents, by reacting two solutions at room
temperature to form a durable foam with significantly greater
volume in a matter of minutes. This process requires no caustic or
dangerous reagents during the foam synthesis step and uses the
alcoholic/phenolic OH groups on the extract and reacts them in
standard fashion with a di-isocyanate cross-linking agents to
produce a non-differentiated poly-urethane having good thermal
capability as well as reasonable toughness, tensile strength and
elasticity. This process also takes advantage of the
alcoholic/phenolic OH groups on graphene oxide produced from coal
via the Hummer's method or graphitic coal char produced from coal.
The addition of graphene oxide or graphitic coal char would greatly
increase the strength of the coal PMC.
[0076] Experimentally produced coal extract is made in a continuous
Soxhlet process using a standard evaporator, condenser and
filter/syphon scheme with dimethylformamide as the solvent. A
portion of the coal extract is then pyrolysed at 850.degree. C. for
10-15 minutes in wet air and then crushed to a 200-mesh size. As a
laboratory example, graphene oxide is produced via the standard
Hummer's method from coal. A mixture of 0.5 g of water and 1% (w/w
%) graphene oxide or 1% (w/w %) graphitic coal char, 0.1 g of
dibutyltin dilaurate and 2 g of the coal extract is be prepared.
Approximately 14 g of toluene d-isocyanate is added to the mixture
and stirred by hand vigorously, which causes the solution to foam,
after which is allowed to cool to room temperature.
Production of Polyamides from Coal
[0077] Described is a process that produces polyamides from organic
coal extracts without intermediate separation of the extract into
its individual chemical or boiling point range constituents. This
process takes advantage of the carboxylic acid groups on the
extract and reacts them in standard fashion with a diamine
cross-linking agents to produce a non-differentiated polyamides
having good thermal capability as well as reasonable toughness,
tensile strength and elasticity.
[0078] Coal extract is made by suspending coal in a high
temperature, high pressure tetralin. The dissolved extract
precipitates from solution as the temperature and pressure is
reduced. As a laboratory scale example, 0.5 g of the solid extract
is then dissolved in DMF and heated under reflux at 130.degree. C.
for 4 hours with a 0.5 g of hexamethylene diamine. The solution is
then placed in a heated petri dish and the DMF evaporated to
produce deposits of the polyamide.
[0079] A second sample of polyamide is made by suspending 10 g coal
in dimethylformamide at room temperature. This dissolved extract is
separated by filtration from the solids and then directly reacted
with 0.5 g of hexamethylene diamine at 150.degree. C. and 1
atmosphere pressure. The solution was refluxed for 4 hours and
placed in a heated petri dish to form the polyamide deposit as
above.
[0080] By varying chemical composition, reaction conditions and
solvent systems, engineered polyamides can be produced that have
different physical, chemical and intrinsic properties, like
flexibility, tensile strength, glass transition temperature of the
resulting polymer.
Conductive Composite Derived from Coal
[0081] There is a current technical need for organic composite
materials which have sufficient electrical conductivity to shield
the electromagnetic emission coming from computer CPU's, cell
phones, microwave ovens and the like. High cost thermoplastics
filled with moderate cost carbon black is commonly used, but the
market is looking for fillers with higher conductivity at lower
fill volume. Graphene and multi or single walled carbon nanotubes
function perfectly in this role; however, their high price prevents
them from achieving widespread use. A coal based carbon particle
with a prolate or oblate shape may achieve a lower volume fill in
an electrically conductive composite at a significantly lower
price.
[0082] Described is a three step process to make an electrically
conductive organic composite system consisting of a coal based
derived polymeric matrix composite (PMC) that utilizes a coal based
polymeric base with a second, coal based, carbon filler to form an
electrically conductive composite.
[0083] The process scheme consists of 3 stages, namely 1)
Extraction of organic residue, 2) Conversion of resulting solid to
functionalized graphitic char, and 3) Reacting the residue and
functionalized char with a di-isocyanate to make a urethane based
polymeric composite.
[0084] Experimentally, the coal residue is extracted using DMF as a
solvent at temperatures up to 450.degree. C. where temperatures
over 150.degree. C. require a pressure vessel with increased volume
of extract yield attainable with increasing temperature. This
solution is then used in making the composite. The solids remaining
after the residue extraction are pyrolysed at 850.degree. C. for
10-15 minutes and the char is then ground to a 200-mesh size and
further ground on a ball mill with ethanol added as a carrier
fluid. After milling for 16 hours, the char is filtered to remove
the solvent and then placed in a stainless steel bomblet with 1/10
equivalent weights of a di-isocyanate. The bomblet is sealed and
heated to 400.degree. C. to functionalize the char. The char is
then washed with several aliquots of acetone to remove the excess
di-isocyanate and dried.
Polyesters Derived from Coal
[0085] Described is a process that produces polyesters from organic
coal extracts without intermediate separation of the extract into
its individual chemical constituents. This process takes advantage
of the carboxylic acid groups on the extract and reacts them in
standard fashion with a diol cross-linking agents to produce a
non-differentiated polyesters having good thermal capability as
well as reasonable toughness, tensile strength and elasticity.
[0086] Coal extract is made by suspending coal in a high
temperature, high pressure tetralin. The dissolved extract
precipitates from solution as the temperature and pressure are
reduced. Experimentally, 0.5 g of the solid extract is dissolved in
DMF and heated under reflux at 130.degree. C. for 4 hours with a
0.35 g of ethylene glycol. The solution is then placed in a heated
petri dish and the DMF evaporated to produce deposits of the
polyester.
[0087] A second sample of urethane is made by suspending 10 g coal
in dimethylformamide at room temperature and the extract is
separated by filtration from the solids and then directly reacted
with 0.35 g of ethylene glycol at 150.degree. C. and 1 atmosphere
pressure. The solution was refluxed for 4 hours and placed in a
heated petri dish to form the polyester deposit as above.
[0088] To control desirable properties, substitution of other
glycols such as propylene glycol, benzenediol, or bisphenol may
result in a similar polymer and that in combination with mixtures
of diols can be used to control desirable properties, like
flexibility, tensile strength, glass transition temperate, of the
resulting polymer.
Structural Foam Composite
[0089] Described is a multi-step process, including: 1) Liquid
Extraction of polar organic residue from low rank coals, 2)
Distillation or other separation of the polar extract to recover
high volatile organics and toluene and other selected aromatics, 3)
Conversion of these remaining aromatics to di-isocyanates via
acidic nitration followed by hydrogenation, followed by phosgene
carboxylation, 4) Conversion of the remaining solid to
functionalized graphitic char and 5) Reacting the residue, the
di-isocyanate and functionalized char to make a urethane based
polymeric composite.
[0090] The coal residue is extracted using DMF as a solvent at
temperatures up to 450.degree. C. where temperatures over
150.degree. C. require a pressure vessel and the volume yield of
extract increases with temperature. Prior to reacting to form the
composite, the concentration of residue in the solvent should
approach 1 g residue/2 g solvent. i.e. as close to saturation as
possible. This solution is used to make the composite.
[0091] Toluene is nitrated in a HNO.sub.3/H.sub.2SO.sub.4 solution
and the di-nitrate hydrogenated to the di-amine with hydrogen at
500.degree. C. in a pressure vessel. The diamine is converted to
di-isocyanante by exposure to phosgene at 250.degree. C.
[0092] The solids remaining after the residue extraction are then
pyrolysed at 850.degree. C. for 10-15 minutes in wet air and then
crushed to a 200-mesh size. This powder is further ground on a ball
mill with ethanol added as a carrier fluid. After milling for 16
hours, the char is filtered to remove the solvent and then placed
in a stainless steel bomblet with equal weight of extracted residue
and equal (residue+char) weight of the di-isocyanate. The bomblet
is sealed and heated to 180.degree. C. to form the composite.
[0093] The resulting foam had a density of 0.33 g/cc and a crush
strength>150 PSI.
Urethanes from Coal
[0094] Described is a process that produces urethanes from organic
coal extracts without intermediate separation of the extract into
its individual chemical constituents. This process reacts
alcoholic/phenolic OH groups on the extract a with a di-isocyanate
cross-linking agents to produce a non-differentiated polyurethane
having good thermal capability as well as reasonable toughness,
tensile strength and elasticity.
[0095] Experimentally, coal extract was made by suspending coal in
a high temperature, high pressure tetralin solution, whereby the
dissolved extract precipitated from solution as the temperature and
pressure were reduced. Experimentally, 0.5 g of the solid extract
is then dissolved in acetone and heated under reflux at 60.degree.
C. for 4 hours with a 0.25 g of toluene di-isocyanate. The solution
is then placed in a heated petri dish and the acetone evaporated to
produce films of the urethane. A second sample of urethane is made
by suspending 10 g coal in dimethylformamide at room temperature.
This dissolved the extract is separated by filtration from the
solids and then directly reacted with 0.5 g of toluene
di-isocyanate at 150.degree. C. and 1 atmosphere pressure. The
solution is refluxed for 4 hours and placed in a heated petri dish
to form the urethane film as above.
[0096] A third sample is made identically to sample 2 with the
exception that 2 drops of di-butyl tin dilaurate is added to the
isocyanate mixture as a catalyst and the solution is refluxed for
only 1 hour prior to placing in a dish to evaporate the
solvent.
[0097] Substitution of other di-isocyanates such as
1,6-diisocyanato hexane may result in a similar polymer and that
mixtures of isocyanates can be used to control desirable
properties, like flexibility, tensile strength, glass transition
temperate, of the resulting polymer.
Graphene/Graphene Oxide Films and Powders Derived from Coal
[0098] Described is a multi-step process for the synthesis of
graphene powders and films from coal as well as outlining a pathway
to synthesize graphite oxide powders and reduced graphene oxide
films from coal. The process includes: 1) Volatile burn off of
organic material from coal for 30 minutes at 850.degree. C. and 2)
High temperature graphitization in an inert, vacuum environment of
resulting solids via induction heating (>2500.degree. C.) of a
graphite crucible that contains the resulting solid from step
1.
[0099] The graphene powder or film is then produced by: 3) Tip/bath
sonication of resulting material in spray friendly solvents
(ethanol and isopropyl alcohol), 4) Centrifugation of the material
to select nanoflake material in supernatant followed by decanting
of solution to remove the bottom solid material, 5) Vacuum drying
of the supernatant produces graphene flake powder (powder
synthesis), 6) Forced nebulization of supernatant from step 4 onto
heated substrates to form conductive films of variable thickness
and conductivities, and 7) Synthesized films were then further
annealed via tube furnace annealing from 800-1450.degree. C. (Film
synthesis).
[0100] Alternatively, graphite oxide powder and graphene oxide
films may be produced via: 3) Oxidation of material using strong
oxidizer for variable time or until violent oxidation of solution
occurs. The oxidizing solution consisted of 98% sulfuric acid,
potassium permanganate, and sodium nitrate, 4) The solids are
collected via centrifugation and washed 3.times. with deionized
water with each wash followed by centrifugation and 5) The solution
supernatant was discarded and the solids dried via freeze drying
(Powder synthesis).
Example 7--Proximate and Ultimate Analysis
[0101] Analysis of Pyrolysis Char
[0102] Sample ID: CE-16-Pc (Char)
TABLE-US-00006 TABLE 6 Proximate and Ultimate Analysis of Pyrolysis
Char (Refer to Example 2, Table 1) As Received Moisture Moisture
& Ash ASTM wt % Free wt % Free wt % Method Proximate Analysis
Moisture 1.55 ***** ***** D7582 Ash 11.46 11.64 ***** D7582
Volatile 24.98 25.37 28.71 D7582 Matter Fixed Carbon 62.02 62.99
71.29 calculated Total 100.00 100.00 100.00 Ultimate Analysis
Moisture 1.55 ***** ***** D7582 Ash 11.46 11.64 ***** D7582 Carbon
73.89 75.05 84.93 D5373 Hydrogen 3.34 3.39 3.83 D5373 Nitrogen 3.87
3.93 4.45 D5373 Sulfur 0.45 0.46 0.52 D4239 Oxygen 5.45 5.53 6.26
calculated Total 100.00 100.00 100.00 As Received Moisture Moisture
& Ash ASTM Btu/lb Free Btu/lb Free Btu/lb Method Heating 12,237
12,430 14,067 D5865 Value
[0103] Hydrogen and Oxygen values reported do not include hydrogen
and oxygen in the free moisture associated with sample. Reported
results calculated by ASTM D3180. Results are an average of 2
runs.
Analysis of Pyrolysis Char Form the Pyrolyzed Residue of the
Solvent Extracted Coal
[0104] Sample ID: CE-13-Res-Pc (Char)
TABLE-US-00007 TABLE 7 Proximate and Ultimate Analysis of Pyrolysis
Char where pyrolysis occurred post solvent extraction (Refer to
Example 4, Table 4) As Received Moisture Moisture & Ash ASTM wt
% Free wt % Free wt % Method Proximate Analysis Moisture 1.07 *****
***** D7582 Ash 13.22 13.36 ***** D7582 Volatile 25.59 25.87 29.86
D7582 Matter Fixed Carbon 60.11 60.77 70.14 calculated Total 100.00
100.00 100.00 Ultimate Analysis Moisture 1.07 ***** ***** D7582 Ash
13.22 13.36 ***** D7582 Carbon 70.81 71.58 82.63 D5373 Hydrogen
3.41 3.45 3.98 D5373 Nitrogen 1.27 1.29 1.49 D5373 Sulfur 0.21 0.21
0.24 D4239 Oxygen 10.00 10.11 11.67 calculated Total 100.00 100.00
100.00 As Received Moisture Moisture & Ash ASTM Btu/lb Free
Btu/lb Free Btu/lb Method Heating 11,549 11,674 13,475 D5865
Value
[0105] Hydrogen and Oxygen values reported do not include hydrogen
and oxygen in the free moisture associated with sample. Reported
results calculated by ASTM D3180. Results are an average of 2
runs.
Analysis of Residue from the Solvent Extraction of the Pyrolysis
Char Tested in Table 6
[0106] Sample ID: CE-16-Res
TABLE-US-00008 TABLE 8 Proximate and Ultimate Analysis of solvent
extraction residue of the sample (CE-16-Res) tested in Table 6
(Refer to Example 4, Table 3) As Received Moisture Moisture &
Ash ASTM wt % Free wt % Free wt % Method Proximate Analysis
Moisture 0.50 ***** ***** D7582 Ash 10.11 10.16 ***** D7582
Volatile 23.59 23.70 26.38 D7582 Matter Fixed Carbon 65.81 66.14
73.62 calculated Total 100.00 100.00 100.00 Ultimate Analysis
Moisture 0.50 ***** ***** D7582 Ash 10.11 10.16 ***** D7582 Carbon
75.25 75.63 84.18 D5373 Hydrogen 3.69 3.71 4.13 D5373 Nitrogen 1.41
1.41 1.57 D5373 Sulfur 0.34 0.34 0.38 D4239 Oxygen 8.71 8.75 9.74
calculated Total 100.00 100.00 100.00 As Received Moisture Moisture
& Ash ASTM Btu/lb Free Btu/lb Free Btu/lb Method Heating 12,572
12,635 14,063 D5865 Value
[0107] Hydrogen and Oxygen values reported do not include hydrogen
and oxygen in the free moisture associated with sample. Reported
results calculated by ASTM D3180. Results are an average of 2
runs.
TABLE-US-00009 TABLE 9 Quality Control Reference % Parameter
Material Expected Result Recovery Ash AR2775 6.80 6.32 93 Volatile
Matter AR2775 37.77 39.6 105 Carbon hs-10006a 65.6 63.64 97
Hydrogen hs-10006a 6.69 6.72 100 Nitrogen hs-10006a 8.2 8.45 103
Sulfur AR1701 0.53 0.55 104 Heating Value, Benz 1 11,373 11,413 100
Btu/lb
STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS
[0108] All references, including publications, patent applications,
and patents, cited herein are hereby incorporated by reference to
the same extent as if each reference were individually and
specifically indicated to be incorporated by reference and were set
forth in its entirety herein.
[0109] The use of the terms "a" and "an" and "the" and "at least
one" and similar referents in the context of describing the
invention (especially in the context of the following claims) are
to be construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. The
use of the term "at least one" followed by a list of one or more
items (for example, "at least one of A and B") is to be construed
to mean one item selected from the listed items (A or B) or any
combination of two or more of the listed items (A and B), unless
otherwise indicated herein or clearly contradicted by context. The
terms "comprising," "having," "including," and "containing" are to
be construed as open-ended terms (i.e., meaning "including, but not
limited to,") unless otherwise noted. Recitation of ranges of
values herein are merely intended to serve as a shorthand method of
referring individually to each separate value falling within the
range, unless otherwise indicated herein, and each separate value
is incorporated into the specification as if it were individually
recited herein. All methods described herein can be performed in
any suitable order unless otherwise indicated herein or otherwise
clearly contradicted by context. The use of any and all examples,
or exemplary language (e.g., "such as") provided herein, is
intended merely to better illuminate the invention and does not
pose a limitation on the scope of the invention unless otherwise
claimed. No language in the specification should be construed as
indicating any non-claimed element as essential to the practice of
the invention.
[0110] Preferred embodiments of this invention are described
herein, including the best mode known to the inventors for carrying
out the invention. Variations of those preferred embodiments may
become apparent to those of ordinary skill in the art upon reading
the foregoing description. The inventors expect skilled artisans to
employ such variations as appropriate, and the inventors intend for
the invention to be practiced otherwise than as specifically
described herein. Accordingly, this invention includes all
modifications and equivalents of the subject matter recited in the
claims appended hereto as permitted by applicable law. Moreover,
any combination of the above-described elements in all possible
variations thereof is encompassed by the invention unless otherwise
indicated herein or otherwise clearly contradicted by context.
[0111] All references throughout this application, for example
patent documents including issued or granted patents or
equivalents; patent application publications; and non-patent
literature documents or other source material; are hereby
incorporated by reference herein in their entireties, as though
individually incorporated by reference, to the extent each
reference is at least partially not inconsistent with the
disclosure in this application (for example, a reference that is
partially inconsistent is incorporated by reference except for the
partially inconsistent portion of the reference).
[0112] The terms and expressions which have been employed herein
are used as terms of description and not of limitation, and there
is no intention in the use of such terms and expressions of
excluding any equivalents of the features shown and described or
portions thereof, but it is recognized that various modifications
are possible within the scope of the invention claimed. Thus, it
should be understood that although the present invention has been
specifically disclosed by preferred embodiments, exemplary
embodiments and optional features, modification and variation of
the concepts herein disclosed may be resorted to by those skilled
in the art, and that such modifications and variations are
considered to be within the scope of this invention as defined by
the appended claims. The specific embodiments provided herein are
examples of useful embodiments of the present invention and it will
be apparent to one skilled in the art that the present invention
may be carried out using a large number of variations of the
devices, device components, methods steps set forth in the present
description. As will be obvious to one of skill in the art, methods
and devices useful for the present methods can include a large
number of optional composition and processing elements and
steps.
[0113] When a group of substituents is disclosed herein, it is
understood that all individual members of that group and all
subgroups, including any isomers, are disclosed separately. When a
Markush group or other grouping is used herein, all individual
members of the group and all combinations and subcombinations
possible of the group are intended to be individually included in
the disclosure. When a compound is described herein such that a
particular isomer of the compound is not specified, for example, in
a formula or in a chemical name, that description is intended to
include each isomers of the compound described individual or in any
combination. Additionally, unless otherwise specified, all isotopic
variants of compounds disclosed herein are intended to be
encompassed by the disclosure. For example, it will be understood
that any one or more hydrogens in a molecule disclosed can be
replaced with deuterium or tritium. Isotopic variants of a molecule
are generally useful as standards in assays for the molecule and in
chemical and biological research related to the molecule or its
use. Methods for making such isotopic variants are known in the
art. Specific names of compounds are intended to be exemplary, as
it is known that one of ordinary skill in the art can name the same
compounds differently.
[0114] Many of the molecules disclosed herein contain one or more
ionizable groups [groups from which a proton can be removed (e.g.,
--COOH) or added (e.g., amines) or which can be quaternized (e.g.,
amines)]. All possible ionic forms of such molecules and salts
thereof are intended to be included individually in the disclosure
herein. With regard to salts of the compounds herein, one of
ordinary skill in the art can select from among a wide variety of
available counterions those that are appropriate for preparation of
salts of this invention for a given application. In specific
applications, the selection of a given anion or cation for
preparation of a salt may result in increased or decreased
solubility of that salt.
[0115] Every formulation or combination of components described or
exemplified herein can be used to practice the invention, unless
otherwise stated.
[0116] Whenever a range is given in the specification, for example,
a temperature range, a pressure range, a time range or a
composition or concentration range, all intermediate ranges and
subranges, as well as all individual values included in the ranges
given are intended to be included in the disclosure. It will be
understood that any subranges or individual values in a range or
subrange that are included in the description herein can be
excluded from the claims herein.
[0117] All patents and publications mentioned in the specification
are indicative of the levels of skill of those skilled in the art
to which the invention pertains. References cited herein are
incorporated by reference herein in their entirety to indicate the
state of the art as of their publication or filing date and it is
intended that this information can be employed herein, if needed,
to exclude specific embodiments that are in the prior art. For
example, when composition of matter are claimed, it should be
understood that compounds known and available in the art prior to
Applicant's invention, including compounds for which an enabling
disclosure is provided in the references cited herein, are not
intended to be included in the composition of matter claims
herein.
[0118] As used herein, "comprising" is synonymous with "including,"
"containing," or "characterized by," and is inclusive or open-ended
and does not exclude additional, unrecited elements or method
steps. As used herein, "consisting of" excludes any element, step,
or ingredient not specified in the claim element. As used herein,
"consisting essentially of" does not exclude materials or steps
that do not materially affect the basic and novel characteristics
of the claim. In each instance herein any of the terms
"comprising", "consisting essentially of" and "consisting of" may
be replaced with either of the other two terms. The invention
illustratively described herein suitably may be practiced in the
absence of any element or elements, limitation or limitations which
is not specifically disclosed herein.
[0119] One of ordinary skill in the art will appreciate that
starting materials, biological materials, reagents, synthetic
methods, purification methods, analytical methods, assay methods,
and biological methods other than those specifically exemplified
can be employed in the practice of the invention without resort to
undue experimentation. All art-known functional equivalents, of any
such materials and methods are intended to be included in this
invention. The terms and expressions which have been employed are
used as terms of description and not of limitation, and there is no
intention that in the use of such terms and expressions of
excluding any equivalents of the features shown and described or
portions thereof, but it is recognized that various modifications
are possible within the scope of the invention claimed. Thus, it
should be understood that although the present invention has been
specifically disclosed by preferred embodiments and optional
features, modification and variation of the concepts herein
disclosed may be resorted to by those skilled in the art, and that
such modifications and variations are considered to be within the
scope of this invention as defined by the appended claims.
* * * * *